Organometallics p. 2417 - 2430 (1989)
Update date:2022-09-26
Topics:
Baralt, Eduardo
Boudreaux, Edward A.
Demas, James N.
Galen Lenhert
Lukehart
McPhail, Andrew T.
McPhail, Donald R.
Myers Jr., James B.
Sacksteder, LouAnn
True, William R.
The results of a comprehensive investigation of the chemistry of the diplatinum compound [Pt2(μ-C=CHPh)(C≡CPh)(PEt3)4]BF 4 (1) and related derivatives are presented. Complex 1 reacts with halides, NCS-, and various RS- nucleophiles to give the neutral compounds [Pt2(μ-C=CHPh) (C≡CPh) (PEt3)3X] with loss of one PEt3 ligand. These Pt2X complexes react with acid and X- nucleophile to give the neutral compounds [Pt2(μ-C=CHPh) (PEt3)3X2] upon loss of phenylacetylene. The X-ray structures of the Pt2Cl, Pt2I, and Pt2Br2 complexes have been determined. [Pt2(μ-C=CHPh)(C≡CPh)(PEt3)3Cl]: monoclinic; P21/c; Z = 4; a = 11.685 (1) A?, b = 20.810 (7) A?, c = 19.172 (4) A? β = 123.96 (1)°. [Pt2(μ-C=CHPh)-(C≡CPh)(PEt3)3I]: orthorhombic; Pbca; Z = 8; a = 18.004 (3) A?, b = 22.805 (4) A?, c = 19.328 (4) A?. [Pt2(μ-C=CHPh)(PEt3)3Br2]: monoclinic; Cc; Z = 8; a = 10.359 (1) A?, b = 33.054 (9) A?, c = 19.855 (5) A? β= 93.40 (2)°. SC-MEH-MO calculations of the electronic structure of compound 1 indicate a large negative charge on each of the Pt atoms which is reminiscent of the results reported earlier from similar calculations on the anion Pt2(P2O5H2)4 4-. Similarities between the photochemistry of the complexes reported herein and that known for Pt2(P2O5H2)44- are presented. Complex 1 reacts with MeI under photolysis to give Pt2I and Pt2I2, and it reacts as a catalyst under photolysis to produce acetone and molecular hydrogen from 2-propanol. The complex Pt2Cl emits a red-orange luminescence at 696 nm in a 4:1 ethanol/methanol matrix at 77 K upon excitation at 410 nm. This luminescent state has an average lifetime of 1.7 μs and is attained with an "optical" quantum yield of 0.010 (2).
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(1988)