Arsines metal complexes

Tertiary arsines have been widely employed as ligands in a variety of transition metal complexes (74), and they appear to be useful in synthetic organic chemistry, eg, for the olefination of aldehydes (75). They have also been used for the formation of semiconductors (qv) by vapor-phase epitaxy (76), as catalysts or cocatalysts for a number of polymeri2ation reactions (77), and for many other industrial purposes. 

Although trialkyl- and triarylbismuthines are much weaker donors than the corresponding phosphoms, arsenic, and antimony compounds, they have nevertheless been employed to a considerable extent as ligands in transition metal complexes. The metals coordinated to the bismuth in these complexes include chromium (72—77), cobalt (78,79), iridium (80), iron (77,81,82), manganese (83,84), molybdenum (72,75—77,85—89), nickel (75,79,90,91), niobium (92), rhodium (93,94), silver (95—97), tungsten (72,75—77,87,89), uranium (98), and vanadium (99). The coordination compounds formed from tertiary bismuthines are less stable than those formed from tertiary phosphines, arsines, or stibines. 

C. A. McAuliffe and W. Levason, Phosphine, Arsine and Stibine Complexes of the Transition Elements, Elsevier, Amsterdam, 1979, 546 pp. A review with over 2700 references. See also C. A. McAuliffe (ed,), Transition-Metal Complexes of Phosphorus, Arsenic and Antimony Donor Ligands, Macmillan, London, 1972,... 

An investigation of the chelate effect the binding of bidentate phosphine and arsine chelates in square-planar transition metal complexes. D. M. A. Minahan, W. E. Hill and C. A. McAuliffe, Coord. Chem. Rev., 1984, 55, 31-54 (153). 

V. Other Metal Complexes of Tertiary Phosphines and Arsines Containing one Olefinic Group... 

Oxovanadium(IV) complexes with dithiophosphate ligands have been extensively examined <8,121.161,252,386) x typical ESR spectrum is shown in Fig. 7. In addition to the eight vanadium 1=112 hyperfine lines phosphorus (/ = 1/2) superhyperfine splitting is also observed. The phosphorus superhyper-fine splitting can be considered a bit unusual since the phosphorus is located about 3 A or more away from the metal ion. P and As superhyperfine splitting has been observed in the ESR spectra of ill-defined vanadium phosphine 388) and arsine 389) complexes but in those cases, presumably, direct V-P and V—As interactions occur. ESR parameters have been tabulated for a large number of dithiophosphate 121,252) dithiophosphinate 121.252) complexes. Evaluation 3i) of the fractional 3s character of unpaired electron in dithiophosphate complexes yielded a value of 1.35%. The vanadyl(IV) complexes possess approximate C2V symmetry. The unpaired d electron resides... 

The As—N bond is labile and this has been widely exploited in synthetic arsenic chemistry. Some idea of the versatility168 can be seen from Schemes 1 and 2. Refluxing secondary amines with tris(dimethylamino)arsine effects transamination (equation 6). These tris(dialkyl-amino)arsines undergo the general reactions in Scheme 1, enabling ready access to a wide variety of compounds, many of them finding use as ligands in transition metal complexes (see Chapter 14 of this work). 

Arsine, 3-dimethylarsinopropylbis(but-3-enyl)-, 1010 Arsine, dimethylphenyl-, 1006 Arsine, ethylenebis(dichloro-, 1005 Arsine, ethylenebis(dimethyl-, 1006 Arsine, ethylenebisfdiphenyl-, 1006 Arsine, ethylidynetris(methylenebis dimethyl-, 1007 Arsine, iododimethyl-, 1005 Arsine, methyldiphenyl-, 1006 Arsine, o-phenylenebis(dichloro-, 1005 Arsine, o-phenylenebis(dimethyl-, 1006 metal complexes, 499... 

Mohr, F., Priver, S.H., Bhargava, S.K. and Bennett, M.A. (2006) Ortho-metallated transition metal complexes derived from tertiary phosphine and arsine ligands. Coord. Chem. Rev., 250,... 

Lobana, Tarlok, S., Structure and Bonding of Metal Complexes of Tertiaryphosphine-Arsine Chalcogenides Including Analytical, Catalytic,... 

The ligands that have been used in the preparation of metal nitride complexes are quite varied. They include halides, carbogenic groups (alkyl moiety and Cp ), pnic-togens (amine, amide, imide, phosphine, and arsine), and chalcogens (ether, alkox-ide, oxo, thioalkoxide, and selenides). Chart 1 provides a listing of the various ligands and the associated nitrido metal complexes. 

Transition metal complexes catalyze desulfurization of thiiranes. Complexes of Rh <1986TL3573>, Re <1997TL7701, 1999CC1003>, and Mo <2003JA3871> have been successfully employed in catalytic quantities. The presence of a stoichiometric sulfur acceptor such as carbon monoxide or an alkene, phosphine, or arsine is required. In Re-catalyzed desulfurization, the formation of an intermediate Re =S species via initial coordination of the thiirene ligand has been suggested (Schemes 12 and 13) <1997TL7701>. Kinetics and mechanism of sulfur... 

Oxidative addition of Hj to cationic metal complexes can occur with replacement of coordinated ligands e.g., [Ir(CO)3L2]BPh (L = tertiary phosphine or arsine) are prepared by passing CO through trans-[IrCl(CO)LJ solutions in the presence of... 

Polydentate olefin substitution has been studied mainly in Group VIB metal complexes. The compound Mo(CO)4(7r-CgHi2) undergoes substitution (87, 88) with l,2-bis(diphenylphosphino)ethane, 2,2 -dipyridyl, 1,10-phenanthroline, and triphenylphosphine, -arsine, and -stibine, producing Mo(CO)4L2 or Mo(CO)4D, where L and D are, respectively, the mono- and bidentate ligands. The reaction rate is described by the equation... 

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