Synthesis, Reactions, and Nuclear Magnetic Resonance Studies of Some Substituted arachno-Decaborane and arachno-Nonaborane Derivatives, and the Isolation of Novel Polyhedral Diplatinaboranes. Crystal and Molecular Structure of 3-B2H5)(η3-B6H9)>

DOI: 10.1039/DT9860002433

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2433 - 2442 (1986)

Update date:2022-09-26

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Authors:

Ahmad, Rohana

Crook, Janet E.

Greenwood, Norman N.

Kennedy, John D.

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Article abstract of DOI:10.1039/DT9860002433

Reaction of nido-2-XB10H13 (X=Cl, Br, or I) with SMe2 afforded almost quantitative yields of arachno-2-X-6,9-(SMe2)2-B10H11 which, when heated under reflux with ROH (R=Me or Et), gave moderate yields of arachno-1-X-4-(SMe2)-B9H12 together with the corresponding arachno-4-(SMe2)-7-(OR)-B9H12.Deprotonation of 1-Cl-4-(SMe2)-B9H12 followed by reaction with cis- gave <2-Cl-4,4-(PMe2Ph)2-arachno-4-PtB8H11>.Similar treatment of 4-(SMe2)-7-(OMe)-B9H12 gave the corresponding compound <8-(OMe)-4,4-(PMe2Ph)2-arachno-4-PtB8H11> together with variable (small) yields of the known <(PMe2Ph)2PtB3H7> and , the novel, yellow, air-stable crystalline compound , and a new, green, air-stable compound tentatively formulated as .Single-crystal X-ray diffraction studies on , together with its n.m.r. properties, revealed a novel cluster geometry in which the central almost-linear P-Pt-Pt-P unit is co-ordinated by an η³-B6H9 nido-subcluster and an opposing η³-B2H5 moiety.The crystals are monoclinic, space group P2₁, with a=1618.3(9), b=1330.0(7), c=592.3(3) pm, β=93.62(4)^o, and Z=2.Detailed (1)H, (11)B, and (31)P n.m.r. studies of the various halogen- and alkoxy-substituted platinaboranes are presented, and the mechanistic implications of the observed positions of substitution in the products are discussed.

Full text of DOI:10.1039/DT9860002433

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