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

Journal Article · · Inorganic Chemistry; (United States)
DOI:https://doi.org/10.1021/ic00062a015· OSTI ID:6046501
; ;  [1]
  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), Vol. 32:10; ISSN 0020-1669
Country of Publication:
United States
Language:
English