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Competition between Triborane as a Ligand and a Hybride Donor at Platinum Centres containing Chelating Phosphines: Molecular Structures of PtB3H7>, PtB3H7> and 2>Cl

DOI: 10.1039/DT9910002175

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2175 - 2184 (1991)

Update date:2022-07-29

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Authors:

Haggerty, Brian S.Haggerty, Brian S.

Housecroft, Catherine E.Housecroft, Catherine E.

Rheingold, Arnold L.Rheingold, Arnold L.

Shaykh, Bilal A. M.Shaykh, Bilal A. M.

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Article abstract of DOI:10.1039/DT9910002175

The reaction of 5-C5H4PPh2)2> with the octahydrotriborate(1-) anion, -, leads to both <(L-L)PtB3H7> in which the borane unit acts as a pseudo-bidentate ligand and Cl which results from the borane anion functioning as a hydride donor.For each of the complexes containing a bis(diphenylphosphino)alkane ligand the major product is <PtB3H7>, whereas for the reaction of - with 5-C5H4PPh2)2>, 2>Cl is the predominant species formed.Three productshave been structurally characterised: <PtB3H7> 1, space group P21/c, a = 16.049(4), b = 15.395(4), c = 21.075(5) Angstroem, β = 90.53(2) deg, Z = 8, R = 0.039; <PtB3H7> 3, space group P21, a = 8.8826(18), b = 17.7329(32), c = 9.5520(17) Angstroem, β = 114.115(15) deg, Z = 2, R = 0.032; 2>Cl*3CH2Cl2 6, space group P21/c, a = 12.862(2), b = 38.732(6), c = 14.271(2) Angstroem, β = 99.027(15) deg, Z = 4, R = 0.067.The structure of the cation of 6 resembles that of 2>+ rather than that of t2P(CH2)3PBut2>2>+ thereby indicating that it is the steric bulk of the phosphorus substituents rather than the P-Pt-P bite angle that controls the geometry of the framework and thus the hydride locations.Fenske-Hall molecular orbital calculations have been used to probe the mode of bonding of the hydride ligands to the diplatinum centre.

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