Transition metal promoted reactions of boron hydrides. 13. Platinum catalyzed synthesis of 6,9-dialkyldecaboranes

Journal Article · Wed May 12 04:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00062a015· OSTI ID:6046501

Mazighi, K; Carroll, P J; Sneddon, L G ^[1]

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1. Univ. of Pennsylvania, Philadelphia (United States)

Both chloroplatinic acid and platinum bromide have been found to catalyze the reactions of decaborane(14) with terminal olefins, including ethylene, propylene, 1-butene, and 1-pentene, to give the corresponding 6,9-R[sub 2]B[sub 10]H[sub 12] derivatives in high yields. Chemical studies of 6,9-(n-C[sub 5]H[sub 11])[sub 2]B[sub 10]H[sub 12] (1) show that, in contrast to decaborane(14), 1 does not react to form dibase adducts with the Lewis bases Et[sub 3]N, Ph[sub 3]P, Et[sub 2]S, or MeCN. However, 1 undergoes many other reactions, including deprotonation to 6,9-(n-C[sub 5]H[sub 11])[sub 2]B[sub 10]H[sub 11][sup [minus]], reduction to arachno-6,9-(n-C[sub 5]H[sub 11])[sub 2]B[sub 10]H[sub 12][sup 2[minus]], and degradation to arachno-4-(n-C[sub 5]H[sub 11])B[sub 9]H[sub 13][sup [minus]], analogous to those observed for decaborane(14) when more forcing conditions are employed. Reaction of 6,9-(n-C[sub 5]H[sub 11])[sub 2]B[sub 10]H[sub 12] with trimethylphosphine also results in cage degradation to produce a compound which, based on its NMR data, is proposed to have an arachno-4-(n-C[sub 5]H[sub 11])-6,8-(Me[sub 3]P)[sub 2]B[sub 9]H[sub 10] cage framework structure. Reaction of 6,9-(nC[sub 5]H[sub 11])[sub 2]B[sub 10]H[sub 11][sup [minus]] with (COD)PtCl[sub 2] was found to produce the platinaborane commo-Pt-[nido-7-Pt-8,11-(n-C[sub 5]H[sub 11])[sub 2]B[sub 10]H[sub 10]][sub 2][sup 2[minus]] in good yields. A single-crystal X-ray determination confirmed that the compound has a geometry analogous to that previously confirmed for [B[sub 10]H[sub 12]][sub 2]M[sup 2[minus]] (M = Ni, Pd, Pt) in which the platinum atom occupies a common vertex in two 11-vertex nido-platinaborane clusters. 33 refs., 7 figs., 4 tabs.

• OSTI ID: 6046501
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:10; 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
ALKENES
BASES
BORON COMPOUNDS
BORON HYDRIDES
BROMIDES
BROMINE COMPOUNDS
BUTENES
CATALYSIS
CHEMICAL PREPARATION
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
DECOMPOSITION
DIFFRACTION
ETHYLENE
GEOMETRY
HALIDES
HALOGEN COMPOUNDS
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
LEWIS BASES
MAGNETIC RESONANCE
MATHEMATICS
NUCLEAR MAGNETIC RESONANCE
ORGANIC BORON COMPOUNDS
ORGANIC COMPOUNDS
PENTENES
PLATINUM BROMIDES
PLATINUM COMPLEXES
PLATINUM COMPOUNDS
PROPYLENE
REDUCTION
RESONANCE
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION
YIELDS