Synthesis, structure, and electronic properties of monomeric and dimeric trispyrazolylborate platinum(II) hydride complexes

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Tp ' PtMe(H)(2) (2) [Tp ' = hydridotris(3,5-dimethylpyrazolyl)borate] has been prepared from Tp ' PtMe(CO) (1) via reaction with water in a basic acetone/water mixture. Protonation of 2 at one of the pyrazole nitrogen atoms induces methane elimination, and the resulting platinum(H) monohydride solvent intermediate (3) can be trapped by added ligand. Two chiral cationic platinum(II) monohydride complexes of the type [k(2)-((Hpz*)BHpz*(2),)Pt-(H)(L)][BAr ' (4)] [L = MeCN (4), CH2=CH2 (5); pz* = 3,5-dimethylpyrazolyl, BAr '4 = tetrakis(3,5-trifuoromethylphenyl)borate] have been isolated. If 2 is protonated in the absence of trapping ligand, a deep red hydride-bridged dinuclear complex, [k(2)-((Hpz*)BHpz*(2))Pt(Li-H)](2)[BAr ' (4)](2) (6), forms. DFT calculations supplement intuitive expectations regarding 3-center-2-electron bridging orbital descriptions for the electronic structure of this complex. X-ray structure determinations for the monomeric acetonitrile adduct 4 and the dicationic dimer 6 are reported.
Publisher
AMER CHEMICAL SOC
Issue Date
2001-08
Language
English
Article Type
Article
Keywords

DENSITY-FUNCTIONAL THEORY; FIRST (MU-HYDRIDO)DIPLATINUM(IV) COMPLEX; CATALYTIC REDUCTIVE ELIMINATION; A-FRAME COMPLEXES; METAL-METAL BOND; METHYL(HYDRIDO)PLATINUM(IV) COMPLEXES; REVERSIBLE FORMATION; MOLECULAR-STRUCTURE; TETRAMETHYLPLATINUM(IV) COMPLEX; TRIHYDRIDE COMPLEXES

Citation

INORGANIC CHEMISTRY, v.40, no.18, pp.4726 - 4732

ISSN
0020-1669
DOI
10.1021/ic010099q
URI
http://hdl.handle.net/10203/203375
Appears in Collection
CH-Journal Papers(저널논문)
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