GENERATION OF (MU-ETHYNEDIYL)(METHYLALKOXYCARBENE)DIPLATINUM COMPLEXES FROM REACTION OF CIS,TRANS-[(OC)(C6F5)(2)PT(MU-ETA(2)-C-CSIME(3))PT(C-CSIME(3))L(2)] WITH ROH (R=ET, ME)

被引:18
作者
BERENGUER, JR
FORNIES, J
LALINDE, E
MARTINEZ, F
机构
[1] UNIV ZARAGOZA, CSIC, INST CIENCIA MAT ARAGON, DEPT QUIM INORGAN, E-50009 ZARAGOZA, SPAIN
[2] UNIV LA RIOJA, DEPT QUIM, E-26001 LOGRONO, SPAIN
关键词
D O I
10.1021/om00005a059
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reaction of cis-[Pt(C6F5)2(CO)(THF)I with trans-[Pt(C=CSiMe(3))(2)L(2)], followed by reaction of the neutral mu-eta(2)-monoacetylide-bridged diplatinum intermediates cis,trans-[(OC)(C6F5)(2)-Pt(mu-eta(2)-C=CSiMe(3))Pt(Cxba=CSiMe(3))L(2)] (L = PPh(3) (1), PEt(3) (2)) with alcohols (EtOH, MeOH) yields the (mu-ethynediyl)(methylalkoxycarbene)diplatinum species cis,trans-[(OC)(C6F5)(2)-Pt-C=C-Pt{C(Me)OR}L(2)] (L = PPh(3), R = Et (3a), Me (3b); L = PEt(3), R = Et (4a), Me (4b)), resulting from unexpected rearrangement chemistry involving bridging and terminal (trimethylsilyl)acetylide ligands. The X-ray molecular structure of the complex cis,trans-[(oc)(C6F5)(2)Pt-C=C-Pt{C(Me)OEt}(PEt(3))(2)] (4a) has been determined. It crystallizes in the monoclinic system, space group P2(1)/c with a = 15.216(3) Angstrom, b = 14.197(4) Angstrom, c = 18.167(5) Angstrom, beta = 107.99(2)degrees, V = 3733(2) Angstrom(3),, and Z = 4. The two coordination planes around the platinum atoms adopt an almost eclipsed arrangement (dihedral angle 6.7 degrees) rather than the staggered form found in similar diplatinum complexes.
引用
收藏
页码:2532 / 2537
页数:6
相关论文
共 56 条
[21]   I+-ABSTRACTION VERSUS I--DISPLACEMENT IN THE REACTIONS OF DIIODOACETYLENE WITH METAL-CARBONYL ANIONS - X-RAY STRUCTURE OF [(OC)5MNC=CMN(CO)5] [J].
DAVIES, JA ;
ELGHANAM, M ;
PINKERTON, AA ;
SMITH, DA .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1991, 409 (03) :367-376
[22]  
Davies S G, 1990, ADV ORGANOMET CHEM, V30, P1
[23]   SYNTHESIS OF NEW HYDRIDE-CARBYNE AND HYDRIDE-VINYLCARBYNE COMPLEXES OF OSMIUM(II) BY REACTION OF OSH2CL2(P-I-PR3)2 WITH TERMINAL ALKYNES [J].
ESPUELAS, J ;
ESTERUELAS, MA ;
LAHOZ, FJ ;
ORO, LA ;
RUIZ, N .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (11) :4683-4689
[24]   PREPARATION OF DOUBLY ACETYLIDE-BRIDGED BINUCLEAR PLATINUM PLATINUM AND PLATINUM PALLADIUM COMPLEXES - STRUCTURES OF [((DPPE)PT(CCPH)2)PT(C6F5)2] AND (PMEPH3)2[(C6F5)2PT(MU-CCPH)2PT(C6F5)2] [J].
FORNIES, J ;
GOMEZSASO, MA ;
LALINDE, E ;
MARTINEZ, F ;
MORENO, MT .
ORGANOMETALLICS, 1992, 11 (08) :2873-2883
[25]   DINUCLEAR AND TRINUCLEAR PLATINUM COMPLEXES WITH DOUBLE ACETYLIDE BRIDGES - MOLECULAR-STRUCTURE OF [NBU(4)](2)[PT-3(C6F5)(4)(MU-C-CPH)(4)]CENTER-DOT-4THF (THF=TETRAHYDROFURAN) [J].
FORNIES, J ;
LALINDE, E ;
MARTIN, A ;
MORENO, MT .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1994, (02) :135-141
[26]   RUTHENIUM TUNGSTEN AND IRON TUNGSTEN COMPLEXES WITH ETHYNYL AND ETHYNEDIYL BRIDGES [J].
FRANK, KG ;
SELEGUE, JP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (17) :6414-6416
[27]   NOVEL CATIONIC VINYLIDENE COMPLEXES OF IRON(II) CONTAINING FE(ETA-C5H5)L2 AS METAL AUXILIARY (L2 = BIS(DIPHENYLPHOSPHINO)METHANE (DPPM) AND BIS(DIMETHYLPHOSPHINO)METHANE (DMPM)) - CRYSTAL-STRUCTURE OF [FE(=C=C(ME)PH)(ETA-C5H5)(DPPM)]I [J].
GAMASA, MP ;
GIMENO, J ;
LASTRA, E ;
MARTIN, BM ;
ANILLO, A ;
TIRIPICCHIO, A .
ORGANOMETALLICS, 1992, 11 (03) :1373-1381
[28]   REACTIONS OF CATIONIC VINYLIDENE COMPLEXES [FE(=C=C(R1)R2)(ETA-C5H5)(DPPM)]+ [DPPM = BIS(DIPHENYLPHOSPHINO)METHANE] WITH NUCLEOPHILES - STEREOSELECTIVE SYNTHESIS AND CRYSTAL-STRUCTURE OF THE ALKENYL COMPLEX (E)-[FE(C(H)=C(ME)PH)(ETA-C5H5)(DPPM)] [J].
GAMASA, MP ;
GIMENO, J ;
LASTRA, E ;
LANFRANCHI, M ;
TIRIPICCHIO, A .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1992, 430 (02) :C39-C43
[29]  
HARTLEY FR, 1982, COMPREHENSIVE ORGANI, V6, P508
[30]   HYDROCARBON-BRIDGED COMPLEXES .15. MOLECULAR AND ELECTRONIC-STRUCTURES OF (MU-ETHYNEDIYL)BIS(PENTACARBONYLRHENIUM), (OC)5REC=CRE(CO)5 [J].
HEIDRICH, J ;
STEIMANN, M ;
APPEL, M ;
BECK, W ;
PHILLIPS, JR ;
TROGLER, WC .
ORGANOMETALLICS, 1990, 9 (04) :1296-1300