Polyhedral iridamonocarbaborane chemistry. Two ten-vertex arachno-6,9-iridacarbadecaboranes and some related ten-vertex carbaborane chemistry. Comparative nuclear magnetic resonance studies and the molecular structure of [asym-9-(CO)-9,9-(PPh3)2-9-H-arachno-9,6-IrCB8H12]
- 1 January 1990
- journal article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 9,p. 2887-2894
- https://doi.org/10.1039/dt9900002887
Abstract
Reaction of trans-[IrCl(CO)(PPh3)2] with [NMe4][nido-6-CB9H12] in solution resulted in the formation in low yields of two isomers (sym and asym) of [9-(CO)-9,9-(PPh3)2-9-H-arachno-9,6-IrCB8H12]. These new air-stable yellow compounds differ in the arrangement of the exopolyhedral {(CO)(PPh3)2H} ligand group on the metal atom. Single-crystal X-ray diffraction analysis on the asym isomer confirmed the molecular constitution. Crystals were monoclinic, space group Cc, with a= 1 112.7(2), b= 2 184.7(3), c= 1 553.2(2) pm, β= 94.06(1)°, and Z= 4; 3 265 observed data [I > 2.0σ(I)]; R= 0.0183, R′= 0.0187. The cluster structure is of arachno ten-vertex ‘boat’ configuration, with the {Ir(CO)(PPh3)2} and {CH2 centres occupying the “prow” positions 9 and 6, and with the Ir–H hydrogen atom being endo over the cluster open face. N.m.r. spectroscopy permits assignment of the cluster 11B and 1H parameters and thence comparison with the equivalent parameters of the analogues [B10H14]2–, [6-CB9H14]–, 6,9-C2B8H14, and [5-(η5-C5H5)-5,6,9-CoC2B7H11], in order to assess the comparative effects of replacement of boron by carbon and metal centres in the basic ten-vertex arachno[B10H14]2– cluster type. Preparative details for [arachno-6-CB9H14]– are given.Keywords
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