Polyhedral metallacarbaborane chemistry: preparation, molecular structure, and nuclear magnetic resonance investigation of [3-(η5-C5Me5)-closo-3,1,2-MC2B9H11] (M = Rh or Ir)
- 1 January 1990
- journal article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 2,p. 681-689
- https://doi.org/10.1039/dt9900000681
Abstract
Reaction between Cs[nido-7,8-C2B9H11] and [{M(η5-C5Me5)Cl2}2] (M = Rh or Ir) yielded orange-yellow, air-stable crystals of [3-(η5-C5Me5)-closo-3,1,2-RhC2B9H11] [compound (2), 34%] or [3-(η5-C5Me5)-closo-3,1,2-IrC2B9H11] [compound (3), 96%] both of which were characterized by their assigned 11B and 1H n.m.r. spectra and by single-crystal X-ray diffraction analyses. Crystals of (2) were orthorhombic, space group P212121, with a = 1 081.0(2), b = 1 278.2(1), c = 1 278.4(2) pm, and Z = 4; R = 0.0197, R′ = 0.0204 for 1 756 observed reflections [I > 2.0σ(I)]. Crystals of (3) were also orthorhombic, space group P212121, with a = 1 076.3(1), b = 1 282.9(1), c = 1 292.8(2) pm, and Z = 4; R = 0.0286, R′ = 0.0307, for 1 712 observed reflections [I > 2.0σ(I)]. The n.m.r. properties of the C2B9H11 fragments of (2) and (3) are compared with the 11B and hitherto unreported 1H n.m.r. characteristics of the corresponding fragments of [3-(η5-C5H5)-closo-3,1,2-CoC2B9H11] (4), closo-1,2-C2B10H12, nido-7,8-C2B9H13, and [nido-7,8-C2B9H12]−, in order to assess any n.m.r. shielding patterns that might reveal bonding trends. The unique endo/bridging open-face hydrogen atom in [nido-7,8-C2B9H12]− is discussed in the light of its n.m.r. properties.Keywords
This publication has 37 references indexed in Scilit:
- Assigned cluster11B and1H NMR properties of [3‐(η6‐C6Me6)‐closo‐3,1,2‐RuC2B9H11]Magnetic Resonance in Chemistry, 1989
- Open cluster configurations of [1,1-(PPh3)2-1-H-1,2,4-IrC2B8H10] and other formally Wadian 24-electron 11-vertex speciesInorganic Chemistry, 1989
- Facile pathway-defined fluxional cluster isomerization in ten-vertex closo-2,1,6-metalladicarbaboranes of ruthenium and rhodiumJournal of the Chemical Society, Chemical Communications, 1988
- The unexpected open cluster structure of [1-(.eta.6-MeC6H4CHMe2-4)-2,4-Me2-1,2,4-RuC2B8H8]Organometallics, 1987
- Quantitative thermal rearrangement of an eleven-vertex metalladicarbaborane to give the isomeric cluster nido-[2-(η6-C6Me6)-8,10-Me2-2,8,10-OsC2B8H8] with an unexpected BCBCB open faceJournal of the Chemical Society, Chemical Communications, 1987
- Two-dimensional boron-11-boron-11 nuclear magnetic resonance spectroscopy as a probe of polyhedral structure: application to boron hydrides, carboranes, metallaboranes, and metallacarboranesJournal of the American Chemical Society, 1984
- Carbaborane derivatives of the late- and post-transition elements. Part 2. Dicarbaundecaboranyl compounds of copper(I), gold(I), and mercury(II); the crystal and molecular structure of 3-triphenylphosphine-3-mercura-1,2-dicarbadodecaborane(II), a pseudo-σ-bonded metallacarbaboraneJ. Chem. Soc., Dalton Trans., 1979
- Molecular and crystal structure of 3,3-bis(triethylphosphine)-1,2-di-carba-3-platinadodecaborane(11), and molecular-orbital analysis of the ‘slip’ distortion in carbametallaboranesJ. Chem. Soc., Dalton Trans., 1978
- X-Ray crystallographic and theoretical studies on ‘slipped’ metallacarboranesJournal of the Chemical Society, Chemical Communications, 1977
- Deuteration and spectroscopic studies of (3)-1,2- and (3)-1,7-dicarba-nido-dodecahydroundecaborate(1 -) and (3)-1,2-dicarba-nido-undecaborane(13)Inorganic Chemistry, 1971