DISTORTIONS IN 6-CO-ORDINATE COMPLEXES OF MOLYBDENUM(II) AND TUNGSTEN(II) - CRYSTAL-STRUCTURES OF MER-[MO(SC6H2PR3I-2,4,6)(2)(CO)(3)(PMEPH(2))], CIS,CIS,CIS-[W(SC(6)H(2)ME(3)-2,4,6)(2)(CO)(2)-(PME(2)PH)(2)] AND [W(SEC6H3PR2I-2,6)(2)(CO)(2)(PME(2)PH)(2)]

被引:25
作者
BURROW, TE [1 ]
HUGHES, DL [1 ]
LOUGH, AJ [1 ]
MAGUIRE, MJ [1 ]
MORRIS, RH [1 ]
RICHARDS, RL [1 ]
机构
[1] UNIV SUSSEX,NITROGEN FIXAT LAB,BRIGHTON BN1 9RQ,E SUSSEX,ENGLAND
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1995年 / 08期
关键词
D O I
10.1039/dt9950001315
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The red, diamagnetic complexes mer-[Mo(SC6H2Pr3i-2,4,6)(2)(CO)(3)(PMePh(2))] 1 and [Mo(SC6H2Pr3i- 2,4,6)(2)(CO)(2)(PMePh(2))(2)] 2 have been prepared by reaction of [MoH(SC6H2Pr3i-2,4,6)(3)(PMePh(2))] with CO in tetrahydrofuran, The crystal structure of 1 shows it to have a distorted octahedral geometry with mer-CO ligands [d(Mo-S) 2.380(1) and 2.366(1); d(Mo-C) 2.030(5). 2.026(4) and 2.066(5); d(Mo-P) 2.561(1) Angstrom; large S-Mo-S angle of 116.0 degrees]. Reaction of CO with [WH(SC(6)H(2)Me(3)-2,4,6)(3)(PMe(2)Ph)(2)] in toluene gives green, distorted octahedral cis,cis,cis-[W(SC(6)H(2)Me(3)-2,4,6)(2)(CO)(2)(PMe(2)Ph)(2)] 3 [d(W-S) 2.379(2) and 2.385(2); d(W-C) 1.967(7) and 1.991(8); d(W-P) 2.556(2) and 2.507(2) Angstrom]. Reaction with [WH(SeC6H3Pr2i-2,6)(3)(PMe(2)Ph)(2)] gives burgundy, [W(SeC6H3Pr2i-2,6)(2)(CO)(2)(PMe(2)Ph)(2)] 4 [d(W-Se) 2.506(1) and 2.583(1); d(W-C) 1.942(8) and 1.943(8); d(W-P) 2.467(2) and 2.471(2) Angstrom]. The physical properties of 1-4 and the structures of 1, 3 and 4 are discussed in terms of their distortions from regular octahedral or trigonal-prismatic geometries. A method of classifying such structures is proposed.
引用
收藏
页码:1315 / 1323
页数:9
相关论文
共 24 条
  • [1] DINITROGEN COMPLEXES OF TUNGSTEN WITH BULKY PHOSPHINE CO-LIGANDS - PREPARATION AND CRYSTAL-STRUCTURES OF [(W(N2)2(PET2PH)3)2(MU-N2)], TRANS-[W(N2)2(PET2PH)4].C4H8O, AND "[W(ETA-6-C6H5PPRN2)(N-2)(PPRN2PH)2] AND THEIR REACTIONS TO GIVE HYDRAZINE OR AMMONIA
    ANDERSON, SN
    RICHARDS, RL
    HUGHES, DL
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1986, (02): : 245 - 252
  • [2] [Anonymous], 1974, INT TABLES XRAY CRYS, VIV, p[99, 149]
  • [3] RHENIUM NITROSYL COMPLEXES WITH SIMPLE AND WITH STERICALLY DEMANDING AROMATIC THIOLATE LIGANDS - X-RAY CRYSTAL-STRUCTURES OF [PPH4][RE2(SC6H4-ME-4)7(NO)2].CH2CL2 AND [RE(SC6H3PRI2-2,6)4(NO)]
    BLOWER, PJ
    DILWORTH, JR
    HUTCHINSON, JP
    ZUBIETA, JA
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1985, (08): : 1533 - 1541
  • [4] RELATIVE PHOSPHORUS LIGAND SIZES FROM CIS-TRANS DISTRIBUTIONS OF W(CO)4(L)(L') PRODUCTS OBTAINED FROM THE REACTION OF W(CO)4(L)(PY) WITH L' (L AND L' = PHOSPHINES), REACTION-KINETICS, AND SYNTHESES OF STARTING MATERIALS
    BOYLES, ML
    BROWN, DV
    DRAKE, DA
    HOSTETLER, CK
    MAVES, CK
    MOSBO, JA
    [J]. INORGANIC CHEMISTRY, 1985, 24 (20) : 3126 - 3131
  • [5] MONOHYDRIDE COMPLEXES OF MOLYBDENUM(IV) AND TUNGSTEN(IV) CONTAINING BULKY THIOLATE LIGANDS - X-RAY CRYSTAL-STRUCTURES OF [MH(SC6H2PRI3-2,4,6)3(PME2PH)2], M = MO OR W
    BURROW, TE
    HILLS, A
    HUGHES, DL
    LANE, JD
    MORRIS, RH
    RICHARDS, RL
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1991, (07): : 1813 - 1820
  • [6] STRUCTURE OF DIMETHYL(PHENYL)PHOSPHONIUM TRIS(1,2-BENZENEDITHIOLATO)TUNGSTEN(V)
    BURROW, TE
    MORRIS, RH
    HILLS, A
    HUGHES, DL
    RICHARDS, RL
    [J]. ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1993, 49 : 1591 - 1594
  • [7] REACTIONS OF THE HYDRIDETHIOLATE COMPLEXES [MH(SC6H2R3-2,4,6)3(PME2PH)2] (M = MO OR W, R = ME OR PR-I) - X-RAY CRYSTAL-STRUCTURES OF [M(SC6H2PRI(3)-2,4,6)2(CO)2(PME2PH)2] (M = MO OR W)
    BURROW, TE
    LOUGH, AJ
    MORRIS, RH
    HILLS, A
    HUGHES, DL
    LANE, JD
    RICHARDS, RL
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1991, (10): : 2519 - 2526
  • [8] HYDRIDE COMPLEXES OF MOLYBDENUM AND TUNGSTEN IN A SULFUR ENVIRONMENT
    BURROW, TE
    LAZAROWYCH, NJ
    MORRIS, RH
    LANE, J
    RICHARDS, RL
    [J]. POLYHEDRON, 1989, 8 (13-14) : 1701 - 1704
  • [9] BURROW TE, 1993, THESIS U TORONTO
  • [10] THIOLATE COMPLEXES OF OSMIUM(III) WITH TERTIARY PHOSPHINES AND THEIR DICARBONYL DERIVATIVES OF OSMIUM(II) - X-RAY CRYSTAL-STRUCTURE OF TRANS,TRANS,TRANS-[OS(SC6F5)2(CO)2(PET2PH)2]
    CRUZGARRITZ, D
    SOSA, P
    TORRENS, H
    HILLS, A
    HUGHES, DL
    RICHARDS, RL
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1989, (03): : 419 - 423