949094-32-0Relevant articles and documents
Preparation, characterization, and structural systematics of diphosphane and diarsane complexes of gallium(III) halides
Cheng, Fei,Hector, Andrew L.,Levason, William,Reid, Gillian,Webster, Michael,Zhang, Wenjian
, p. 7215 - 7223 (2007)
The diphosphane o-C6H4(PMe2)2 reacts with GaX3 (X = Cl, Br, or I) in a 1:1 molar ratio in dry toluene to give trans-[GaX2{o-C6H4(PMe 2)2}2][GaX4], the cations of which contain the first examples of six-coordinate gallium in a phosphane complex. The use of a 1:2 ligand/GaCl3 ratio produced [GaCl2{o-C 6H4(PMe2)2}][GaCl4], containing a pseudotetrahedral cation, and similar pseudotetrahedral [GaX 2{o-C6H4(PPh2)2}] [GaX4] complexes are the only products isolated with the bulkier o-C6H4(PPh2)2. On the other hand, Et2P(CH2)2PEt2, which has a flexible aliphatic backbone, formed [(X3Ga)2{μ-Et 2P(CH2)2PEt2}], in which the ligand bridges two pseudotetrahedral gallium centers. The diarsane, o-C 6H4(AsMe2)2, formed [GaX 2{o-C6H4(AsMe2)2}] [GaX4], also containing pseudotetrahedral cations, and in marked contrast to the diphosphane analogue, no six-coordinate complexes form; a very rare example where these two much studied ligands behave differently towards a common metal acceptor. The complexes [(I3Ga)2{μ-Ph 2As-(CH2)2AsPh2}] and [GaX 3(AsMe3)] are also described. The X-ray structures of trans-[GaX2{o-C6H4(PMe2) 2}2][GaX4] (X = Cl, Br or I), [GaCl 2{o-C6H4(PPh2)2}] [GaCl4], [GaX2{o-C6H4(AsMe 2)2}][GaX4] (X = Cl or I), [(I 3Ga)2{μ-Ph2-As(CH2) 2AsPh2}], and [GaX3(AsMe3)] (X = Cl, Br or I) are reported, and the structural trends are discussed. The solution behavior of the complexes has been explored using a combination of 31P{1H} and 71Ga NMR spectroscopy.
