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By E. Peters

Roasting processes are divided into several elementary mechanisms, any of which could be significant or pre-dominant in a particular roast. The elementary processes considered in-elude beat transfer, gas-solid inter-actions with accompanying mass transfer between the bed and furnace atmosphere, vapor phase transport processes in solid-solid interactions, and solid phase diffusion processes. Examples are chosen of processes in which one of these mechanisms pre-dominates and some recently obtained data is presented to support the existence and significance of these mechanisms. Proposals are also made for future research in these areas, and for utilizing the information in the improvement of roaster capacities’ OASTING of ores as a preparative treatment for smelting or leaching has been practiced for so long that its origin has been lost in antiquity, but little has been under-stood of its basic nature until fair-ly recent times. The nominal chemistry of roasting processes is now understood; that is, the initial chemical com-pounds present in the ores or con-

Jan 1, 1961

By M. Sagedahl

The off gas from a smelter is cooled and dust removed in an electrostatic precipitator before approximately 95% of the sulphur dioxide (S02) is converted to sulfuric acid. However, the tail gas may need to be polished to remove the rest S02 to meet demands. A flue gas desulphurization (FGD) system, as usually applied to S02 removal on coal and oil fired Power Station, is suitable for polishing tail gases from copper smelters. The ALSTOM Seawater FGD process makes use of the alkalinity in the seawater to absorb and neutralize S02. Before being returned to the sea, the seawater is treated to comply with environmental regulations. As the ALSTOM Seawater FGD process uses no reagent and produces no byproduct, it is extremely cost-effective for coastal installations. The first SWFGD plant started operation in 1968. Over 60 of these units have been installed worldwide. The ALSTOM Seawater FGD process removes S02 from flue gas flows corresponding to a total of 70,000,000 Nm3 /h. Suitable for thermal power stations, smelters and oil refineries, ALSTOM Seawater FGD plants efficiently treats flue gases in the range of 300,000 Nm3/h to 2, 700,000 Nm3 /h per FGD plant, containing 20 - 6,500 ppm of S02.

Jan 1, 2007

By A. M. Esteves

This paper offers an overview of local content policies and practice in the mining sector. Specifically, the paper aims to answer the question of how national and regional governments, industry and civil society can work together to seek an optimal outcome while pursuing their diverse objectives. The paper begins by defining local content and its scope at the subnational level. Specific recommendations for the design of local content policies to mitigate social, economic and governance risks are developed. The document then offers some recommendations regarding the role of partners in design, implementation, monitoring, and enforcement of local content policies.

Aug 1, 2013

By P. Clinton Milne

Uranium mines in Washington State include the producing Midnite and Sherwood mines and several mined-out deposits, the most productive of which was the Daybreak mine. The Midnite mine is generally classified as a hydrothermal deposit consisting of tabular orebodies in Precambrian pelitic and calcareous metasedimentary host rocks. The host rocks occur as roof pendants in a Cretaceous porphyritic quartz monzonite intrusive; the quartz monzonite averages 12 ppm U308 The uranium deposit appears to have undergone a complex genesis, involving a series of depositional and enrichment stages. The Sherwood uranium deposit, approximately 4 miles south of the Midnite mine, occurs near the bottom of a basal Late Cretaceous to Paleocene arkosic conglomerate. The conglomerate lies nonconformably on the porphyritic quartz monzonite that is associated with the Midnite deposit. The Sherwood and Midnite uranium deposits may have had a similar genetic history linked by a common uraniferous pluton source, ground-water action, and/or leaching of uranium-rich ash flows from now-eroded, overlying, Eocene volcanics. The Daybreak deposit, in northeastern Spokane County, consists entirely of secondary uranium mineralization (metaautunite) in a quartz monzonite pluton. Mineralization is confined to a low-angle fault zone and is most highly concentrated at the intersection of primary and secondary shears. Both hydrothermal and ground-water origins are feasible. Besides the Midnite-Sherwood area, 14 other areas in the western Okanogan Highlands physiographic province and Cascades region have favourable characteristics for uranium potential. Criteria include the existence of uranium occurrences, Tertiary basin sediments with intercalated volcanic and volcaniclastic rocks, favourable geochemical data, alkaline plutons associated with uranium occurrences or borders of Tertiary basins, and structural controls.

Jan 1, 1979

By Jolanta Olkowska-Oetzel

Reactions of gold?phosphino complexes [(AuX)(PR3)] (X= Cl, Br, I; R = organic rest) with Se(SiMe3)2 lead to the formation of gold complexes with chalcogenide bridges. The reaction of the complex Ph3PAuCl and tBuSe(SiMe3) gives the cluster [Au5Se2(PPh3)4]Cl 1. The in situ preparation of the complex [(AuCl)2dpph] (dpph = Ph2P(CH2)6PPh2) by reaction of dpph with Me2SAuCl, and subsequent reaction with Se(SiMe3)2 leads to the formation of [(Au3Se)2(dpph)3]Cl2 2. Reactions of the gold(I) complex [(AuCl)2dpppe], (dpppe = Ph2P(CH2)5PPh2) with Se(SiMe3)2 and InCl3 in different molar ratios lead to the formation of [Au10Se4(dpppe)4]InCl5 3 and [Au4(SeInCl3)2(dpppe)2] 4. The reaction of [(AuCl)2dpph] with Te(SiMe3)2 and GaCl3 produces the isostructural cluster compound [Au4(TeGaCl3)2(dpph)2] 5. From the reaction of Se(SiMe3)2 with [(AuCl)2dppe] (dppe = Ph2P(CH2)2PPh2) and InCl3 [Au8Se4In(dppe)4](InCl4)3 6 can be isolated. The structures of 1 - 6 were determined by X?ray diffraction.

Oct 1, 2003

By T. A. Wedge

This paper suggests a crude correction for the impact of raw material quality on factor productivity in the Canadian mining industry. Such a correction would give a figure more dependent on the changing efficiency of the use of labour and capital, and less dependent on the effects of unquantified changes in inputs.

Jan 1, 1973

By C. S. Lord

"AbstractThe slow progress of conventional geological reconnaissance of the northern Canadian Shield during the past twenty years clearly indicates the need for a radically new field technique. Operation Keewatin, involving the use of helicopters as the traversing vehicles, was planned and executed by the Geological Survey of Canada in response to this requirement.About 57,000 square miles of District of Keewatin, N.W.T., were mapped during the 1952 field season in appropriate detail for publication at 1 inch to 8 miles. The Operation disclosed about 14,100 square miles of Precambrian sedimentary and volcanic rocks ranging in •age from Archaean to Late Proterozoic. About 7,700 square miles of this area are underlain by greenstone. This work was accomplished in a field season of 113 days, including the spring break-up. Routine aerial geological observations were made from two helicopters flying about 300 feet above the ground; these observations were checked by more than 1,700 landings and about an equal number of aerial observations from heights of less than 50 feet. Logistical support was •provided by a Norseman aircraft on skiis or floats. Combined helicopter and Norseman flying time was about 990 hours. More than 1-00 square miles were mapped per helicopter-hour, and about 815 square miles were examined each day that both helicopters operated. The reconnaissance cost about $207,000, or $3.63 per square mile mapped.As a result of this trial use of helicopters there is now available a reasonably proven method whereby an acceptable geological reconnaissance of the barren grounds of the Canadian .Shield within the Districts of Keewatin and Mackenzie might be completed within a decade. Thus, within a few years, it could place at the disposal of the prospecting and mining fraternity data which, by conventional methods, might not be made available to this generation. Due weight must be accorded this time factor when evaluating the aerial technique."

Jan 1, 1953

By J. B. Mawdsley

"AbstractThe uraninite-bearing deposits in the Charlebois Lake area of northeastern Saskatchewan are unusual and important concentrations of uranium. They were first discovered in 1949 and preliminary development work to the end of the 1951 field season indicates the probability that this will become •another uranium producing district. The deposits are in zones bordering granite masses. These zones are of migmatite (mixed rocks) composed of calcium-rich meta-sediments intruded and replaced by a fine-grained white pegmatite. Locally this pegmatite is replaced by an end fraction which is relatively rich in fine-grained disseminated uraninite; it is these occurrences that constitute the bodies of economic interest.The fine-grained white pegmatite contains plagioclase feldspar more lime-rich than that in the granites of which it is an end differentiate. This extra lime, evidently derived from the intruded sediments, would result in the raising of the temperature of crystallization of the pegmatite-forming magma, thus consolidating it rapidly near the granite contacts as a fine-grained pegmatite. The end liquor containing uranium was evidently locally concentrated in minor fracture zones in these pegmatites. Where no lime sediments were present. the coarse-grained alkaline pegmatites were formed. Their crystallization would not be accelerated and the uranium would tend not to be localized in the pegmatite but to migrate and consolidate at lower temperatures with the end products, possibly in some instances as pitchblende veins."

Jan 1, 1952

By Zhou Yanwen, Fudong Wang, Shing Liu

Mixed CrB2 and MoS2 powder (Cr:Mo=1:1 atomic %), without any further process, were used as the targets to be sputtered and deposited onto stainless steel and silicon substrates by pulsed DC power supply. The structures and properties of the CrBMoS films were then analyzed by using SEM, XRD, micro-hardness tester. The SEM morphology of the films showed dense, defect free structure, and the preferred orientations of the films were CrB2 (111) and MoS2 (200) according to XRD spectra. The thicknesses of the films were measured and the relationship between the deposition rates and pulsed factors was determined. The films, with the micro-hardness as high as 19GPa and friction coefficient as low as 0.02, could be considered to be the hard solid lubricant films.

Jan 1, 2015

By M. J. Gole, R. E. T. Hill, S. J. Barnes

"The Agnew (also known as the Perseverance) nickel deposit and its northern extension, the Rocky's Reward deposit, form one of the world's largest accumulations of nickel sulphides hosted by komatiites. Agnew was previously classified as an ""intrusive dunite-associated"" deposit . It has now been shown that the sulphides are hosted by komatiite flows which underlie an adcumulate-textured dunite body that crystallized in a large lava channel.The rocks of the mine area have been subjected to a metamorphic temperature of550°C and pressure of up to 3 kb. The komatiites have mostly been reconstituted to olivine-amphibole chlorite assemblages. There is a zoned sequence of enstatite-, anthophylite-, talc- and antigorite-bearing assemblages inwards from the western margin of the ultramatic reflecting variations in the CO/HP ratio of metamorphic fluids.Facing directions are determined from variations in the proportions of metamorphic minerals and in rock compositions which reflect asymmetric layering in the flows . Olivine-sulphides matrix ore is hosted in a single 50 m thick, east-facing flow that is overlain by flows containing massive sulphides. Much of the massive sulphide has been physically remobilized into fold noses, faults and shear zones. Chemical diffusion of ore components has upgraded a sulphide-rich metasedimentary unit where it is in structural contact with massive ore.To the north, the mineralized flow sequence is separated from a stratigraphically higher komatiite sequence, the Perseverance ultramafic complex, by approximately 150 m of felsic meta volcanic and meta sedimentary rocks. Southward, the Perseverance ultramafic grades laterally into an olivine adcumulate body and its lower contact cuts progressively down stratigraphy until it lies directly on top of olivine-sulphide ore of the mineralized flow sequence. This discordant contact is interpreted as the base of a thermal erosion channel formed by a voluminous komatiite lava flow. This contact greatly influenced later deformation of the mineralized flow sequence."

Jan 1, 1989

By G. W. Clark

"The mining of the ore bodies at Rabbit Lake has in the past been by the open pit method. This method is presently being used to develop the B-zone and will continue into the future with the development of two smaller ore bodies, the A-zone and D-zone. The Eagle Point orebody will be developed by an underground method which will provide production and employment into the next century.The ore bodies at B-zone, A-zone and D-zone are unique in that they are located under Wollaston Lake. To permit mining by the open pit method a steel-celled dyke has been constructed around the north end of the B-zone. This same dyking method will be used for the A -zone and D-zone. INTRODUCTIONMine development at Rabbit Lake commenced in 1970when a detailed engineering feasibility study established the viability of the Rabbit Lake deposit. In 1972 construction of the mill and camp site began. Construction materials were seasonally hauled to the site over a winter road until November 1973when the government of Saskatchewan completed an all-weather road to within six miles of the operation.In October 1974, stripping of the Rabbit Lake open pit began with the removal of overburden and lake bottom sediments from the previously drained Rabbit Lake. The first ore was processed by the mill in June 1975and by October the mill was producing three million pounds per year. The design capacity of five million pounds annually was first achieved in 1977 and maintained until 1981, when lower ore grades resulted in lower production rates .It was clear when mining at Rabbit Lake began that, without additional reserves, the Rabbit Lake operation had a life of less than 10 years. Exploration, therefore, continued in the immediate area in an attempt to discover additional uranium mineralization."

Jan 1, 1989

By Kenneth L. Norris

Stonegate Agricom Ltd. is currently conducting exploration and development drilling of the Paris Hills Phosphate Project (Paris Hills Project) located in Bear Lake County, southeastern Idaho, 3.2 km west of the towns of Paris and Bloomington, Idaho. The project is located adjacent to a highway and 19 km by paved highway to Montpelier, Idaho where the Union Pacific Railroad system is located. Power and water are available locally. The nearest metropolitan centre is Salt Lake City, Utah approximately 225 km by road to the south-west of the property. The Paris Hills Project encompasses an area of approximately 856 hectares. Property holdings consist of three (3) patented lode mining claims and 16 contiguous fee parcels (some with federal phosphate leases). Active open pit phosphate mining operations are located in surrounding counties in south-east Idaho and are owned and operated by Agrium Inc., Monsanto Company and J.R. Simplot Company. The Paris Hills Project is located near the centre of the Western Phosphate Field which constitutes the most extensive phosphorite beds in the United States. Phosphate beds of the Western Phosphate Field occur within the Phosphoria Formation of Permian age and extend over an area of more than 350,000 km2 including extensive areas of Idaho, Utah, Wyoming and Montana. At Paris Hills the phosphate mineralized beds occur in the overturned limb and the horizontal limb of the Paris Syncline. Grades and thicknesses in both the western overturned limb and the eastern horizontal limb of the anticline are similar. The vast majority of potential mineralization occurs in the horizontal limb which underlies most of the property holdings. Mineralization in the overturned limb has a strike length of over three (3) kilometres and extends from the surface to a depth exceeding 300 m depending on location along the north-trending strike of outcrops. Depths of the horizontal limb range from surface along the north side of Bloomington Canyon to estimated depths of 915 to 1,035 m at Paris Canyon. The property contains an Inferred resource of 109.6 million tonnes at 23.6% P2O5 over two mineralized horizons. The phosphate zones have a strike length of over 3 km and extend from surface to a depth of at least 900 m. Drilling commenced late in the 3rd quarter of 2010 and is planned to continue through 2011. The drilling was planned to target an area of potentially higher grade phosphate mineralization and better define and upgrade the current resources.

May 1, 2011

By C. Rocha R.

Petioles is a mining group with integrated operations in the smelting and refining of non-ferrous metals, and is also a chemicals producer. Peñoles is the world's foremost producer of refined silver, metallic bismuth and sodium sulphate and is the leading Latin American producer of refined gold, lead and zinc. The Met-Mex Petioles Zinc Plant commenced operations in 1973 with an annual production capacity of 105,000 t/y. Year after year the production has been increased, and at present, the production capacity is 240,000 t/y. In this paper, the leaching process, particularly the operation of the jarosite circuit and its effective removal of impurities such as arsenic, antimony, indium, selenium and tellurium, is reviewed.

Jan 1, 2006

By T. Verdel, Y. Gunzburger

Rockfalls are major and essentially unpredictable sources of danger, particularly along transportation routes (roads and railways). Thus, the assessment of their probability of occurrence is a major challenge for risk management. From a qualitative perspective, it is known that rockfalls occur mainly during periods of rain, snowmelt, or freeze-thaw. Nevertheless, from a quantitative perspective, these generally assumed correlations between rockfalls and their possible meteorological triggering events are often difficult to identify because i) rockfalls are too rare for the use of classical statistical analysis techniques and ii) all intensities of triggering factors do not have the same probability. In this study, we propose a new approach to investigate the correlation of rockfalls with rain, freezing periods, and strong temperature variations. This approach is tested on three French rockfall databases, the first of which exhibits an outstandingly high frequency of rockfalls (approximately 950 events over 11 years), whereas the other two databases are more typical (approximately 140 events over 11 years). These databases come from (1) the national highway RN1 on La Réunion Island, (2) a railway in the Bourgogne-Franche Comté region, and (3) a railway in the Auvergne region. Whereas a basic correlation analysis is only able to highlight an already obvious correlation in the case of the “rich” database, the newly suggested method appears to detect correlations even in the “poor” ones. Indeed, the use of this method confirms the positive correlation between rainfalls and rockfalls on La Réunion Island database. This method highlights a correlation between cumulative rainfalls and rockfalls in the Bourgogne region, and it detects a correlation between the daily minimum temperature and rockfalls in the Auvergne region. This new approach is easy to use and also serves to determine the conditional probability of rockfall function of a given meteorological factor. This approach will help to optimize risk management in the studied areas based on their meteorological conditions. Nevertheless, even if some rockfalls are correlated to meteorological factors, other seems to occur independently of these factors, which highlights the unpredictability of rockfall hazard.

Jan 1, 2015

By G. G. Campbell

"HistoricalBARYTES was mined in Nova Scotia as early as 1874 from a deposit at Five Islands, on the north shore of Minas Basin. The first record of the presence of the mineral at the Walton site appears in a report by Selwyn in l893, who states: ""Barytes in considerable quantity occurs in veins in lime-stones at Walton and Pembroke"". The exact site of the present workings was marked •on a map published by Fletcher in 1905.The economic •possibilities of this deposit, however, were not recognized until 1940, at which time we were at war with Germany, who up to that time had supplied 50 per cent of the world's requirements.At that time the Nova Scotia Department of Mines, recognizing the need for certain strategic minerals, induced Canadian Industrial Minerals, Limited, to send prospectors into 'the area to look for manganese. No manganese deposits were found, but a deposit of barytes was directed to their attention, and exploration and development work on the occurrence was proceeded with.IntroductionThe south shore of Minas Basin between the Avon river at Windsor and the Stewiacke river at Maitland has long been known as a potential source of mineral wealth. It had attracted the attention of mineralogists and in the past had produced considerable tonnages of manganese ore and gypsum. Depletion of ore in surface and near surface deposits resulted in a dwindling production, until today only deposits of gypsum are worked."

Jan 1, 1952

By M. H. Fathi

The aim of this work was to prepare the metallic coatings on 316L stainless steel dental implant and evaluate the corrosion characteristics and thus the biocompatibility of the uncoated and metallic coated dental implants and comparison of the effect of the type of coatings on biocompatibility. Three types of metallic coatings including Tantalum, Niobium, and Titanium coatings were made using physical vapor deposition process on 316L stainless steel dental implant. Structural characterization techniques including; X-ray Diffraction, Scanning Electron Microscopy and Energy Dispersive X-ray Analysis were utilized to investigate the microstructure and morphology of the coatings. Electrochemical potentiodynamic tests were performed in two types of physiological solutions at 37±1 °C in order to determine and compare the corrosion characteristics. All three types of metallic coatings had a positive effect on improvement of the corrosion behavior so that the coatings could increase the corrosion resistance of 316L stainless steel and this trend was independent to the type of physiological environment. Biocompatible metallic coatings could decrease the corrosion current density that is a distinct advantage for prevention of ion release. This can improve the biocompatibility of the implant and, consequently prevention of tissue damages, inflammation and irritation and obtained desirable histopathological response.

Jan 1, 2007

By Jing Li, Weiqiang Lai, Joe Zhou, Jiezhen Ma, Shuibo Chen, Ashele Copper Company, Feng Gao, Guofu Feng

"Copper-zinc ores often contain gold and silver, which can be recovered into copper concentrate by flotation as by-product. The challenges for operations that produce copper, zinc, gold and silver are the separation of copper and zinc and the low grade of precious metals. Ashele copper-zinc ore in north China contains 2.38% Cu, 0.69% Zn, 0.21 g/t Au and 18.10 g/t Ag and the plant produces copper and zinc concentrates, with gold and silver being recovered into copper concentrate. Copper occurs mainly as chalcopyrite and Zn occurs as sphalerite. Copper is well recovered with a recovery of over 94%. However, the recovery of Zn is substantially low (around 50%) due to fine grain size of sphalerite. In addition, gold recovery is much lower than expected and only 33% of gold in the flotation feed was recovered. The grade of gold in copper concentrate is also lower than the required payable grade (1.0 g/t). To determine the cause for lower Zn and Au recoveries, a plant survey program was conducted on the operation. The information acquired shows that the loss of Zn was mainly in the copper concentrates (accounting for approximately 38% of the head assay); of which, 24% was liberated, 8.5% was associated with chalcopyrite and 4.6% was associated with pyrite, indicating that the separation of copper and zinc was the main cause for the Zn loss, with liberation being the second cause for Zn loss. Future effort in improving Zn recovery should be focused on the separation of zinc from copper. Gold in the ore occurs as both microscopic gold and submicroscopic gold, accounting for 36% and 64% of the head assay, respectively. Microscopic gold occurs mainly as native gold and electrum; it is relatively coarse with a grain size of 10 to 240 µm and a large portion can be recovered by gravity. Submicroscopic gold was mainly carried by pyrite (accounting for 38%), and to a less extent, by tennantite (15%) and chalcopyrite (10%). Gold in sphalerite is nominal (1%). It is suggested that more coarse gold and tennantite be recovered and a gold recovery increase can then be achieved to obtain a copper concentrate with over 1.0 g/t Au through flowsheet optimization. Gravity concentration should be investigated and may be worth added into the existing flowsheet to maximum the gold recovery and grade.INTRODUCTIONCopper-zinc ores containing gold and silver is a subtype of polymetallic sulphide ores. Unlike porphyry copper sulphide ores and iron-oxide copper-gold ores, this type of ores often contains substantial amounts of zinc and lead. Polymetallic sulphide ores are mainly distributed in Canada, such as at the LaRonde and Horne deposits. Other examples include Mt. Morgan in Australia and Boliden in Sweden. Globally, production and reserves from gold-rich VMS deposits account for 1370 t gold. This is equivalent to 1% of the world production and reserves, whereas the Canadian total for gold-rich VMS deposits is 870 t, representing close to 10 % of Canadian production and reserves (Gosselin & Dube, 2005a, 2005b). Flotation is the principal process for processing the copper-zinc sulphides ores, for subsequent smelting, roasting, or hydrometallurgical treatment. Oxidized copper-zinc ores can also be processed using leaching technology. For example, at LaRonde operation (a Cu-Zn-Pb ore containing 3-4 g/t Au and 60-100 g/t Ag) the flowsheet consists mainly of a copper flotation circuit and a zinc flotation circuit followed by a cyanidation process of flotation tails. The precious metals are recovered with copper concentrate, zinc concentrate and cyanidation of zinc tails via Merrill Crowe precipitation (Zhou et al., 2005)."

Jan 1, 2016

By M. S. Badollet, N. W. Edgerton

"A study of the physical properties of long grades of asbestos fibers imported into the United States during the past eight years has disclosed information that will contribute materially to effective selection and use of fibers for electrical products. The study embraced fiber lengths, volume resistivity under three different conditions, total iron by chemical analysis, magnetic rating, conductivity of an aqueous ex-tract and its sodium chloride equivalent.The fibers examined included chrysotiles from Rhodesia, British Columbia, and Barberton area; marlime from Bechuanaland and Province of Quebec; amosite and crocidolites from Africa and Australia; and anthophyllites from Mozambique and from Georgia in the United States. Volume resistivity values provide a relative basis for estimating the electrical performance of end products; magnetic rating -an estimate of the quantity of iron compounds present in excess of those in the asbestos structure; conductivity of an aqueous extract; and an estimate of the ionizable impurities in fibers.Tests of these factors yield in-formation, not heretofore generally known, which may serve as a guide in the evaluation of asbestos fibers for electrical products."

Jan 1, 1960

By A. Rao, J. A. Davidson, B. L. Jones, K. W. Bowes, D. Craib

Supported by ANSTO, Groundwater Science and Inception Consulting Engineers, Boss has embarked on a series of technical projects aimed at reinforcing the Project’s capability to meet its export permit production capability. This paper will focus on three aspects of this technical program: Reducing the cost of resource expansion through smart use of low cost, surface target generation techniques; Improving the rate of uranium leaching and solution stability (gypsum, jarosite) through lixiviant chemistry modifications; and Development of an ion exchange (IX) process to increase production capacity, and integration of IX and the current solvent extraction circuit with the existing uranium precipitation and product preparation circuits.

Jan 1, 2020

By Fabian Mohr

The methyl substituted binuclear cyclometallated gold(I) complexes [Au2(?-n-MeC6H3PPh2)2] [n = 4, 5 and 6] all undergo oxidative addition reactions with halogens and, in the case of the 4- and 5-methyl substituted analogues, with dibenzoyl peroxide to give metal-metal bonded digold(II) complexes [Au2X2(?-C6H3-n-MePPh2)2]. The 4- and 5-methyl substituted digold(II) compounds on warming or exposure to light undergo carbon-carbon coupling reactions to give gold(I) complexes containing the corresponding 2,2'-n,n'-biphenylyldiphenylphosphines. The 6- methyl substituted digold(II) complexes rapidly isomerise above ca. -20° C to binuclear heterovalent gold(I)/gold(III) compounds [XAu(?-2-Ph2PC6H3-6-Me)AuX{?2-(6-MeC6H3-2-PPh2)}], containing a fourmembered cyclometallated ring on a gold(III) centre. Surprisingly, no carbon-carbon coupling could be induced for any of the 6-methyl substituted compounds, even under forcing conditions. This difference in reactivity of the 6- methyl derivative, compared to that of the 5-methyl and unsubstituted analogues was studied by ab initio calculations using a series of model compounds. The results are in excellent agreement with the experimental findings and suggest that the key-step in the C-C coupling reaction is the partial opening of the Au(III)-P bond in one of the transition states. In the 6-methyl system this transition state is energetically inaccessible and hence no C-C coupling occurs.

Oct 1, 2003