Phosphine-arsine complexes

C. A. McAuliffe and W. Levason, Studies in Inorganic Chemistry, Vol. 1, Phosphine, Arsine and Stibine Complexes of the Transition Elements, Elsevier, Amsterdam, The Netherlands, 1979. 

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. 

Tertiary phosphine complexes have been studied intensively since the 1960s. The bulk of the work has been with phosphines, but corresponding arsine complexes are broadly similar. 

Considerable structural information is available on osmium complexes of tertiary phosphines, arsines and stibines (Table 1.13) [152, 157]. 

A considerable number of the tertiary phosphine and arsine complexes of iridium(III) have been synthesized [4, 8] they generally contain 6-coordinate iridium and are conventionally prepared by refluxing Na2IrCl6 with the phosphine in ethanol or 2-methoxyethanol [154]... 

The phosphine and arsine complexes of gold(I) have been intensively studied since the early 1970s. The possibilities of coordination numbers between 2 and 4 have been explored, though the use of bulky ligands is less essential than with the isoelectronic M(PR3)2 (M = Pd, Pt) compounds and the coordination numbers depend on both steric and electronic factors [71]. 

Complexes of the transition metals with phosphines, arsines and stibines. G. Booth, Adv. Inorg. Chem. Radiochem., 1964, 6,1-69 (460). 

Complexes of the Transition Metals with Phosphines, Arsines, and Stibines G. Booth... 

Complexity in the manganese and rhenium pentarbonyl halides substitution arises from the fact that these decompose in inert solvents to form the halogen-bridged dimers [M(CO)4X]2. Both monomers and dimers react with phosphines, arsines, pyridine, aniline etc. to give the disubstituted compounds M(CO)3XL2. Thus three final products or any mixture of them may be obtained, depending upon the precise reaction conditions... 

Detailed procedures for the synthesis of various often used [Ni°L4] complexes (L = phosphines, arsines, stibines, alkyl isocyanides) and [Ni°L 2] complexes (L = bipyridine, phenantroline, diphosphines, diarsines) have been compiled.2413... 

The number of gold complexes containing tertiary phosphines, arsines, or stibines as ligands is large because of the wide use of the fragment AuL+, mainly with L = PPh3, in the synthesis of... 

Considerable structural information is available on osmium complexes of tertiary phosphines, arsines and stibines (Table 1.13) [152, 157], Comparison with data (mainly obtained from EXAFS measurements) on osmium diarsine complexes (Table 1.14) shows that as the oxidation state increases, osmium-halogen bonds shorten whereas Os-P and Os-As bonds lengthen. Bond shortening is predicted for bonds with ionic character,... 

Organolead compounds containing a lead-transition metal bond are also known. When a lead(II) or lead(IV) compound reacts with Co2(CO)gL2 complexes (L = tert -phosphine, -arsine or a phosphite), the blue, air-stable Pb[Co(CO)3L]4 derivatives are obtained371. 

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