Syntheses, structures, and mechanism of formation of trans-chlorohydrobis(trimethylphosphine)plantinum(II) and trans-dihydrobis(trimethylphosphine)platinum(II). Energetics of cis-trans isomerization
The reaction between cis-PtCl/sub 2/(PMe/sub 3/)/sub 2/ (1) and Na(np) (np = naphthalene) under a H/sub 2/ atmosphere yields trans-PtHCl(PMe/sub 3/)/sub 2/ (2). Addition of a second 1 equiv of Na(np) produces cis- and trans-PtH/sub 2/(PMe/sub 3/)/sub 2/ (cis-3 and trans-3). Complex 3 was crystallized in the presence of np to yield trans-3.np. Both the latter complex and 2 were characterized by X-ray diffraction at -145 /sup 0/C. Crystals of 2 belong to the space group P2/sub 1//n with Z = 4, a = 10.241 (5) A, b = 19.012 (11) A, c = 6.300 (4) A, ..beta.. = 96.36 (1)/sup 0/, and V = 1227 (1) A/sup 3/. For the 1259 unique reflections that had I/sub 0/ > 3sigma(I/sub 0/) the Patterson solution and least-squares refinement led to final R = 0.063 and R/sub w/ = 0.082. Crystals of trans-3.np belong to the space group A2/m with Z = 2, a = 6.146 (2) A, b = 10.204 (3) A, c = 14.925 (4) A, ..beta.. = 99.17 (1)/sup 0/, and V = 936 (1) A/sup 3/. For the 864 unique reflections that had I/sub 0/ > 3sigma(I/sub 0/) solution by direct methods and least-squares refinement led to final R = 0.049 and R/sub w/ = 0.062. Complex 2 adopts a square-planar geometry, P(1)-Pt-P(2) = 176.0 (2)/sup 0/, with the Pt-Cl distance, 2.423 (6) A, significantly lengthened because of the trans influence of hydride. The trans-3.np complex exhibits no interaction between trans-3 and np, verifying the role of np as a crystallization agent. Electronic spectra of trans-3/np mixtures in n-hexane solvent did not provide evidence for a charge-transfer complex. Crystals of trans-3.np are extremely sensitive and lose H/sub 2/ under a N/sub 2/ atmosphere. They are stable under a H/sub 2/ atmosphere. 49 references, 3 figures, 5 tables.
- Research Organization:
- Univ. of California, San Diego, La Jolla
- OSTI ID:
- 5953300
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 24:22; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKALI METAL COMPOUNDS
AROMATICS
BOND ANGLE
BOND LENGTHS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORINE COMPLEXES
COHERENT SCATTERING
COMPLEXES
CONDENSED AROMATICS
CRYSTAL STRUCTURE
DATA
DIFFRACTION
DIMENSIONS
ELECTRON SPECTRA
ELEMENTS
EXPERIMENTAL DATA
HYDROCARBONS
HYDROGEN
HYDROGEN COMPLEXES
INFORMATION
ISOMERIZATION
KINETICS
LENGTH
NAPHTHALENE
NITROGEN
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
PLATINUM COMPLEXES
REACTION KINETICS
SCATTERING
SODIUM COMPOUNDS
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION