Issue 11, 1986

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 [Pt2(PMe2Ph)23-B2H5)(η3-B6H9)]

Abstract

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-[PtCl2(PMe2Ph)2] 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 [conjuncto-Pt2(PMe2Ph)2(B6H9)2], the novel, yellow, air-stable crystalline compound [conjuncto-Pt2(PMe2Ph)2(B2H5)(B6H9)], and a new, green, air-stable compound tentatively formulated as [closo-(PMe2Ph)3Pt2B9H8(OMe)]. Single-crystal X-ray diffraction studies on [conjuncto-Pt2(PMe2Ph)2(B2H5)(B6H9)], 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-B6H9nido-subcluster and an opposing η3-B2H5 moiety. The crystals are monoclinic, space group P21, with a= 1 618.3(9), b= 1 330.0(7), c= 592.3(3) pm, β= 93.62(4)°, and Z= 2. Detailed 1H, 11B, and 31P 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.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1986, 2433-2442

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 [Pt2(PMe2Ph)23-B2H5)(η3-B6H9)]

R. Ahmad, J. E. Crook, N. N. Greenwood and J. D. Kennedy, J. Chem. Soc., Dalton Trans., 1986, 2433 DOI: 10.1039/DT9860002433

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