Platinum hydride cluster complexes

Journal Article · Wed May 26 00:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00063a010· OSTI ID:5786098

Ramachandran, R; Puddephatt, R J ^[1]

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1. Univ. of Western Ontario, London (Canada)

The cluster cation [Pt[sub 3]([mu][sub 3]-H)([mu]-dppm)[sub 3]][sup +] (1) is easily and reversibly protonated to give [Pt[sub 3]([mu][sub 3]-H)[sub 2]([mu]-dppm)[sub 3]][sup 2][sup +] (3) or, in the presence of trifluoroacetate, [Pt[sub 3]H([mu][sub 3]-H)([mu]-O[sub 2]CCF[sub 3])([mu]-dppm)[sub 3]][sup +] (4). With a large excess of acid below -60 [degrees]C, the trihydride [Pt[sub 3]([mu][sub 2]-H)[sub 3]([mu]-dppm)[sub 3]][sup 3][sup +] (5) was formed. Complex 3 reacts with CO to give H[sub 2] and the carbonyl cluster cations [Pt[sub 3]([mu][sub 3]-CO)([mu]-dppm)[sub 3]][sup 2][sup +] and [Pt[sub 3]([mu][sub 3]-CO)(CO)([mu]-dppm)[sub 3]][sup 2][sup +], with phosphite ligands P(OR)[sub 3] (R = Me, Et, Ph) to give [Pt[sub 3]H([mu][sub 2]-H)[P(OR)[sub 3]]([mu]-dppm)[sub 3]][sup 2][sup +] (6), and with PPh[sub 3] to give [Pt[sub 2]H(PPh[sub 3])-([mu]-dppm)[sub 2]][sup +]. The new clusters are characterized by multinuclear NMR techniques. The reversible addition of protons to 1 defines a stepwise, bimolecular, electrophilic mechanism of substitution of the Pt[sub 3]([mu][sub 3]-H) ligand.

• OSTI ID: 5786098
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:11; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ATOMIC CLUSTERS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COMPLEXES
HYDRIDES
HYDROGEN COMPOUNDS
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
PHOSPHINES
PHOSPHORUS COMPOUNDS
PLATINUM COMPLEXES
RESONANCE
SYNTHESIS
TRANSITION ELEMENT COMPLEXES