Carborane complexes of ruthenium: Reactions of [Ru(THF)(CO)(2)(eta(5)-7,8-R(2)-7,8-C2B9H9)] (R=H or Me) with alkylidyne complexes of molybdenum and tungsten

被引:27
作者
Anderson, S
Jeffery, JC
Liao, YH
Mullica, DF
Sappenfield, EL
Stone, FGA
机构
[1] BAYLOR UNIV,DEPT CHEM,WACO,TX 76798
[2] UNIV BRISTOL,SCH CHEM,BRISTOL BS8 1TS,AVON,ENGLAND
关键词
D O I
10.1021/om960928t
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The complex [Ru(THF)(CO)(2)(eta(5)-7,8-C2B9H11)] (1a, THF = tetrahydrofuran) reacts with the alkylidyne reagents [M(=CC(6)H(4)Me-4)(CO)(2)(eta(5)-C5H5)] (M = MO Or W) to give the compounds [MRu(mu-CC(6)H(4)Me-4)(CO)(4)(eta(5)-7,8-C2B9H11)(eta(5)-C5H5)] (M = W (2a), Mo (2b)), which readily isomerize to the species [MRu(CO)(4){sigma,eta(5)-9-CH(C(6)H(4)Me-4)-7,8-C2B9H10}(eta(5)-C5H5)] (M = W (3a), Mo (3b)). The structure of 3b was established by X-ray diffraction. The Mo(CO)(2)(eta(5)-C5H5) fragment is attached to the closo-RuC2B9 framework by a Mo-Ru bond and a three-center two-electron B-H-Mo linkage involving a boron atom in an a site in the CCBBB ring ligating the ruthenium. The CH(C(6)H(4)Me-4) moiety bridges between the Ru(CO)(2) group and the B atom located in the other a site in the CCBBB ring. The oxo complex [WRuO{mu-sigma,eta(5)-9-CH(C(6)H(4)Me-4)-7,8-C2B9H10}(CO)(2)(eta(5)-C5H5)] (4a) is a side product in the formation of 3a, and it also was characterized by X-ray diffraction. Treatment of the species 3 with PMe(3) affords the zwitterionic compounds [MRu(CO)(4){eta(5)-9-CH(PMe(3))(C(6)H(4)Me-4)-7,8-C2B9H10}(eta(5)-C5H5)](M = W (5a), Mo (5b)). A single-crystal X-ray diffraction study of 5a revealed that the (OC)(2)W-Ru(CO)(2) unit is bridged by the nido-9-CK(PMe(3))(C(6)H(4)Me-4)-7,8-C2B9H10 group. The open C2B3 face is pentacoordinated to the Ru atom, and there is an exopolyhedral B-H -->-W bond involving a B-alpha atom in the CCBBB ring. The other B-alpha site carries the CH(PMe(3))(C(6)H(4)Me-4) substituent. Reactions between the ruthenium reagent [Ru(THF)(CO)(2)(eta(5)-7,8-Me(2)-7,8-C2B9H9)] (1b) and [W(=CC(6)H(4)Me-4)(CO)(2)(eta(5)-C5H5)] gave [WRuO{mu-sigma,eta(5)-7,8-Me(2)-10-CH2(C(6)H(4)Me-4)-7,8-C2B9H8}(CO)(2)(eta(5)-C5H5)] (4b), [WRu(mu-H){mu-eta(5),eta'(5)- 7,8-Me(2)-9-C5H4-10-CH2(C(6)H(4)Me-4)-7,8-C2B9H7}(CO)(5)](6a), and [WRu{mu-sigma,eta(5)-2,7-Me(2)-8-CH2(C(6)H(4)Me-4)-9-C(H)O-2,7-C2B9H6}(CO)(4)(eta(5)-C5H5)] (7a) that were separated by column chromatography. The corresponding reaction between 1b and [W(=CC(6)H(4)Me-2)(CO)(2)(eta(5)-C5H5)] afforded [WRuO{mu-sigma,eta(5)-7,8-Me(2)-n-CH(C(6)H(4)Me-2)-7,8-C2B9H8}(CO)(2)(eta(5)-C5H5)] (n = 9(4c), 10(4d)) and [WRu{mu-sigma,eta(5)2,7-Me(2)-8-CH2(C(6)H(4)Me-2)-9-C(H)O-2,7-C2B9H6}(CO)(4)(eta(5)-C5H5)](7b). Treatment of 1b with [Mo(=CC(6)H(4)Me-n)(CO)(2)(eta(5)-C5H5)] (n = 4 or 2) yielded [MoRu(mu-H){mu-eta(5),eta'(5)-7,8-Me(2)-9-C5H4-10-CH2(C(6)H(4)Me-n)-7,8-C2B9H7}(CO)(5)] (n = 4 (6b), 2 (6c)). The structures of 4b, 6b, and 7b were established by X-ray diffraction. In 6b, the (OC)(3)Mo(mu-H)Ru(CO)(2) unit is bridged by a 7,8-Me(2)-9-C5H4-10-CH2(C(6)H(4)Me-4)-7,8-C2B9H7 moiety, a structure resulting from a linking of C5H5 and nido-C2B9 groups. The C-5 ring is eta(5)-coordinated to the molybdenum, while the open CCBBB face of the carborane cage is similarly attached to the ruthenium. In complex 7b, a nido-2,7-Me(2)-8-CH2(C(6)H(4)Me-2)-9-C(H)O-2,7-C2B9K6 cage system bridges the Ru-W bond with an eta(5)-CB4 ring coordinated to the Ru atom and with the cage joined to the W atom by a B-W bond. In addition, the C(H)O group forms a second bridge linking the cage to the tungsten, with the latter coordinated by the formyl O atom.
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页码:958 / 971
页数:14
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[1]   Carborane complexes of ruthenium: Studies on the chemistry of the Ru(CO)(2)(eta(5)-7,8-C2B9H11) fragment [J].
Anderson, S ;
Mullica, DF ;
Sappenfield, EL ;
Stone, FGA .
ORGANOMETALLICS, 1996, 15 (06) :1676-1689
[2]   CARBORANE COMPLEXES OF RUTHENIUM - A CONVENIENT SYNTHESIS OF [RU(CO)(3)(ETA(5)-7,8-C2B9H11)] AND A STUDY OF REACTIONS OF THIS COMPLEX [J].
ANDERSON, S ;
MULLICA, DF ;
SAPPENFIELD, EL ;
STONE, FGA .
ORGANOMETALLICS, 1995, 14 (07) :3516-3526
[3]  
ANDERSON S, 1996, ORGANOMETALLICS, V15, P5102
[4]  
[Anonymous], 1974, INT TABLES XRAY CRYS, VIV
[5]   CHEMISTRY OF POLYNUCLEAR METAL-COMPLEXES WITH BRIDGING CARBENE OR CARBYNE LIGANDS .74. SALTS OF THE ANIONS [W(=CC6H4ME2)(CO)2(ETA-5-C2B9H9ME2)]- OR [W(=CC6H3ME2-2,6)(CO)2(ETA-S-C2B9H9ME2)]- AS REAGENTS FOR THE SYNTHESIS OF COMPOUNDS WITH HETERONUCLEAR METAL METAL BONDS - CRYSTAL-STRUCTURE OF [NET4]-[FEW(MU-CC6H3ME2-2,6)(CO)5(ETA-5-C2B9H9ME2)]A [J].
BAUMANN, FE ;
HOWARD, JAK ;
MUSGROVE, RJ ;
SHERWOOD, P ;
STONE, FGA .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1988, (07) :1879-1889
[6]   REACTIONS AT THE METAL VERTEX OF A RUTHENACARBORANE CLUSTER - ACTIVATION OF CARBON-MONOXIDE BY CLOSO-3,3,3-(CO)3-3,1,2-RUC2B9H11 [J].
BEHNKEN, PE ;
HAWTHORNE, MF .
INORGANIC CHEMISTRY, 1984, 23 (21) :3420-3423
[7]   UNIQUE REACTIVITY OF HETERODINUCLEAR PENTACARBONYL(FULVALENE)MOLYBDENUMRUTHENIUM WITH ALKYNES - FLUXIONALITY, REARRANGEMENTS, STRUCTURES, AND 1ST REVERSIBLE CONVERSION OF A SIDE-ON - TO A SEMI-BRIDGING ALKENYLIDENE LIGAND [J].
BOESE, R ;
HUFFMAN, MA ;
VOLLHARDT, KPC .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1991, 30 (11) :1463-1465
[8]   THE INTERPLAY OF ALKYLIDYNE AND CARBABORANE LIGANDS AT METAL CENTERS .2. PROTON-MEDIATED REACTIONS [J].
BREW, SA ;
STONE, FGA .
ADVANCES IN ORGANOMETALLIC CHEMISTRY, VOL 35, 1993, 35 :135-186
[9]   ALKYLIDYNE(CARBABORANE) COMPLEXES OF THE GROUP-6 METALS .3. FACILE TRANSFORMATIONS OF 12-VERTEX AND 13-VERTEX TUNGSTACARBORANE POLYHEDRA - REVERSIBLE FRAMEWORK REARRANGEMENT AND ACID-INDUCED EJECTION OF A CAGE VERTEX [J].
BREW, SA ;
CARR, N ;
JEFFERY, JC ;
PILOTTI, MU ;
STONE, FGA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (06) :2203-2210
[10]   CHEMISTRY OF DI-METAL AND TRI-METAL COMPLEXES WITH BRIDGING CARBENE OR CARBYNE LIGANDS .15. REACTIONS OF THE COMPLEX [W(=CC6H4ME-4)(CO)2(ETA-C5H5)] WITH IRON CARBONYLS - CRYSTAL-STRUCTURES OF [FE2W(MU-3-CR)(MU-CO)(CO)8(ETA-C5H5)] AND [FEW2(MU-3-RC2R)(CO)5L(ETA-C5H5)2] (L=CO OR O) [J].
BUSETTO, L ;
JEFFERY, JC ;
MILLS, RM ;
STONE, FGA ;
WENT, MJ ;
WOODWARD, P .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1983, (01) :101-109