Synthesis and X-ray crystal structure of 3-diethyldithiocarbamato-3-aura-1,2-dicarbadodecaborane. A ‘slipped’ 18-electron metallacarborane

Abstract

Reaction of T1,( 7, 8-C2BgHll) with Et,NCS,AuBr, affords the known ion (1,2-C,B,Hl1),Au-, and also the novel 1 %electron species ( 1, 2-C,BgHll) Au (S,CNEtJ which is shown from X-ray data to have the 'slipped' structure previously found only in 20-or 21-electron systems; a similar structure is also deduced for the 18 electron compound (Ph,P),Pt( l,2-C2BQHll).

Structure of 8-[1,2-dicarba-closo-dodecaboran(12)-3-yl]-5,6-dicarba-nido-decaborane(12)

“…The X-ray study on iso-C4H22B~s has been undertaken in order to clarify the way in which these two dicarbaborane units are connected and to determine the geometry of the molecule. The distances and angles in the 5,6-C2H~B 8 part of the molecule are also of great interest because unsubstituted 5,6-C2H~2B8 has proved to be the important readily available compound from which many new derivatives have been prepared (gtibr, Ple~ek 0567-7408/82/123147-03501.00 & He~m~nek, 1974;Janou~ek, Ple~ek & Plz~tk, 1979;Jung & Hawthorne, 1980;Colquhoun, Greenhough & Wallbridge, 1980). A crystal 0.35 × 0.40 x 0.60 mm was used for data collection on a Syntex P2~ diffractometer with graphite-monochromated Cu K~t radiation.…”

Small cage d10 metallacarboranes: crystal structure of the mercury bridged carborane, μ,μ′-[2-(Si(CH3)3)-3-(CH3)-2,3-C2B4H5]2Hg

“…The former provides a convenient route to B-substituted carboranes [1,2], while the latter is the basis for the construction of the so called ''mercuracarborands'', that are useful in binding anions [3] and have been shown to have catalytic behavior [4]. Mercuracarboranes, where the Hg occupies an apical position above an open face of the carborane, have been reported in the larger, C 2 B 9 cage system [5,6]. However, in these compounds, the Hg atom is slip distorted towards the unique boron on the C 2 B 3 pentagonal face of the carborane, giving an g 3 -(or g 1 ) carborane-metal interaction.…”

Methyltriphenylphosphonium undecahydro-1,2-dicarba-3-thalla-closo-dodecaborate–tetrahydrofuran, [PPh3Me]+[3,1,2-TlC2B9H11]−.1/2(C4H8O), at 173 K

“…T1-C (2) 2.9 I0 (5) C(I)--B(4) 1.650 (9) TI--B (4) 2.743 (6) C(2)--B (7) 1.628 (8) T1-B (7) 2.741 (6) B(7)-B(8) 1.742 (9) TI-B (8) 2.659 (6) B (4) (Hansen, Hazell, Hyatt & Stucky, 1973). (c) 3-(Et2NCS)2-3,1,2-AuC~BqH,, (Colquhoun, Greenhough & Wallbridge, 1976). (d) (Et4N)2+ICu(I,2-C~BgH i,)212- (Wing, 1967).…”

“…There are no unusual intermolecular contact distances. The metal-cage distances, the shortest of which considerably exceeds the sum of the covalent radii, have been discussed in terms of a progressive opening of the metallacarbaborane cage as electron density on the metal increases (Colquhoun, Greenhough & Wallbridge, 1977a). Since the C2B9HI1 cage itself can be regarded essentially as 7,8-C2B9H~i-, the structure provides the best data so far for the parameters of an uncoordinated cage, and confirmation is provided that the framework distortions in 1,2-CzB9H~ metallacarbaboranes (Mingos, Forsyth & Welch, 1977;Colquhoun, Greenhough & Wallbridge, 1976, 1977b, 1978 are produced by coordination of a metal-ligand system to the 7,8-C2B9H~I anion.…”

“…The metal-cage distances, the shortest of which considerably exceeds the sum of the covalent radii, have been discussed in terms of a progressive opening of the metallacarbaborane cage as electron density on the metal increases (Colquhoun, Greenhough & Wallbridge, 1977a). Since the C2B9HI1 cage itself can be regarded essentially as 7,8-C2B9H~i-, the structure provides the best data so far for the parameters of an uncoordinated cage, and confirmation is provided that the framework distortions in 1,2-CzB9H~ metallacarbaboranes (Mingos, Forsyth & Welch, 1977;Colquhoun, Greenhough & Wallbridge, 1976, 1977b, 1978 are produced by coordination of a metal-ligand system to the 7,8-C2B9H~I anion. Furthermore, the framework geometry provides both a reference point for the assessment of such distortions and a con-* Lists of structure factors, anisotropic thermal parameters, bond angles for the anion, bond distances for the cation and solvent, and least-squares-plane calculations have been deposited with the British Library Lending Division as Supplementary Publication No.…”