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ChemInform Abstract: CRYSTAL STRUCTURES OF TRIS(DIETHYLDITHIOCARBAMATO)RHODIUM(III) AND ‐ARSENIC(III)

Chemischer InformationsdienstVolume 7, Issue 8 Organoelement Compounds ChemInform Abstract: CRYSTAL STRUCTURES OF TRIS(DIETHYLDITHIOCARBAMATO)RHODIUM(III) AND -ARSENIC(III) COLIN L. RASTON, COLIN L. RASTONSearch for more papers by this authorALLAN H. WHITE, ALLAN H. WHITESearch for more papers by this author COLIN L. RASTON, COLIN L. RASTONSearch for more papers by this authorALLAN H. WHITE, ALLAN H. WHITESearch for more papers by this author First published: February 24, 1976 https://doi.org/10.1002/chin.197608310AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume7, Issue8February 24, 1976 RelatedInformation

New carbide clusters in the cobalt sub-group. Part III. Crystallographic characterization of the hydroxonium salt of tetradeca-µ-carbonyl-dicarbidotetradecacarbonyl-polyhedro-pentadecarhodate(1–)

The trtle compound crystallizes in the orthorhombic space group Pbcn, with cell constants a= 15.N (2). b= 17.34(2). c= 18.85(2)A, Z= 4. The structure was determined by direct methods from X-ray single-crystai counter data and refined by least-squares calculations to R 0.0267 for 2 387 significant reflections.The [Rh15(CO)28C2]– anion has precise C2 symmetry idealizable to C2v. The Rh15 metal atom cluster can be described as a centted and tetracapped pentagonal prism in which the central atom is twelve-co-ordinated in a non-crystallographicfashion, with Rh–Rh distances ranging from 2.738 to 3.332(3)A. The two carbide-atoms occupy octahedral cavities, mean Rh–C 2.04 A. The carbonyl ligands are bound on the cluster surface, fourteen linearly and fourteen edge-bridging such that all the metal atoms are thrice-connected to the ligands. The molecular architecture is discussed and a growth mechanism of the cluster is proposed.

Crystal structures of tris(diethyldithiocarbamato)-rhodium(III) and -arsenic(III)

The crystal structures of the title compounds, [Rh(CS2·NEt2)3], (I), and [As(CS2·NEt2)3], (II) have been determined by-X-ray diffraction from diffractometer data, and refined by least-squares to R 0.080 (I) and 0.058 (II) for 1 582 and 1 877 reflections. Crystals are monoclinic, space group P21/a, with Z= 4 in unit cells of dimensions : (I)a= 18.07(3), b= 8.276(3), c= 15.80(1)A, β= 96.35(4)°; (II)a= 18.543(4), b= 8.387(2), c= 15.870(3)A, β= 101.05(2)°. The compounds are isomorphous also with the manganese(III) derivative; whereas the MS6 core in (I) is quite close to D3 symmetry (mean Rh–S 2.368A), that of (II) is grossly distorted (as previously described) toward C3 symmetry (mean As–S 2.84 and 2.349A). In (II), the usual equality in the ligand C–S distances is destroyed as a result (mean C–S 1.68 and 1.76 A) and the surrounding angular geometry of the ligand also distorted. The arsenic has a close hydrogen contact (3.2 A) along the pseudo threefold axis from a neighbouring molecule.

New carbide clusters in the cobalt subgroup. Part II. Crystallographic characterization of the di-µ3-carbonyl-hexa-µ-carbonyl-carbidoundecacarbonyl-polyhedro-octarhodium

The title compound crystallizes in the triclinic space group P with cell constants a= 9·18(1), b= 17·76(2), c= 10·46(1)A, α= 75° 57′(6′), β= 69° 4′(6′), γ= 92° 22′(6′), Z= 2. The structure was determined by Patterson and Fourier methods from X-ray single-crystal counter data and refined by block-diagonal least-squares calculations to R 0·0234 for 3423 significant reflections.The molecule has C1 symmetry. The Rh8 metal atom cluster can be described as a monocapped prism plus one edge-bridging atom; Rh–Rh distances range from 2·699 to 2·913(3), mean 2·81 A. The carbide atom occupies the centre of the prism with mean Rh–C 2·127 A. The carbonyl groups are distributed on the cluster surface: two triple bridging, six-edge-bridging, and eleven linearly; their bonding parameters are as expected. The cluster geometry and the ligand stereochemistry suggest the most probable mechanism of formation of the molecule to consist in the insertion of two [Rh(CO)2]+ groups on the [Rh6(CO)15C]2– anion.

Synthesis and crystallographic characterization of the carbidopentadecacarbonylhexarhodate dianion in its bis(benzyltrimethylammonium) salt, the first example of a trigonal prismatic cluster of metal atoms

Carbidopentadecacarbonylhexarhodate dianion has been obtained by reaction of dodecacarbonyltetrarhodium with methanolic sodium hydroxide under carbon monoxide with successive addition of chloroform. The structural characterization has been carried out on the salt [NMe3(CH2Ph)]2[Rh6(CO)15C], which crystallizes in the monoclinic space group C2/c with a= 22·17(2), b= 11·46(1), c= 18·51 (2)A, β= 112° 43′(6′), Z= 4. Diffractometer data have been refined by least-squares methods to a final R of 0·033 for 1654 statistically significant reflections. The anion [Rh6(CO)15C]2– has precise C2 and idealized D3h symmetry. The six rhodium atoms define a trigonal prism whose edges are associated with symmetrical bridging CO groups, the remaining six carbonyl ligands are linearly bonded one per each rhodium atom. The carbide atom occupies the centre of the prism. The mean basal and inter-basal Rh–Rh distances are 2·776(3) and 2·817(2)A respectively; mean Rh–C(carbide) 2·134(6)A. The mean Rh–C and C–O distances for linear, basal bridging, and inter-basal bridging CO groups are 1·89(1), 1·13(1); 2·12(1), 1·14(2); and 2·04(1), 1·17(2)A.