MODELS FOR LINEAR ACETYLIDE POLYMERS - SYNTHESIS AND SINGLE-CRYSTAL X-RAY STRUCTURES OF THE RUTHENIUM(II) ACETYLIDE AND DIACETYLIDES RU(CO)2(PET3)2[(C-EQUIVALENT-TO-C)NR]2 (N = 1, R = ME3SI N = 2, R = ME3SI, H)

被引:103
作者
SUN, Y [1 ]
TAYLOR, NJ [1 ]
CARTY, AJ [1 ]
机构
[1] UNIV WATERLOO, GUELPH WATERLOO CTR GRAD WORK CHEM, DEPT CHEM, WATERLOO CAMPUS, WATERLOO N2L 3G1, ONTARIO, CANADA
关键词
D O I
10.1021/om00060a055
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
As model compounds for long-chain, linear, acetylide-based polymers, the bis(acetylides) and bis (diacetylides) of ruthenium(II) trans-Ru(CO)2(PEt3)2[(C=C)nR], (2, n = 1, R = Me3Si; 3, n = 2, R = Me3Si; 4BAR, n = 2, R = H) have been synthesized and fully characterized by IR and Raman spectroscopy, H-1, C-13{H-1}, and P-31{H-1} NMR studies, and single-crystal X-ray diffraction. Complex 2 crystallizes in the monoclinic space group P2(1)/c with Z = 2 in a unit cell of dimensions a = 11.733 (3) angstrom, b = 10.944 (3) angstrom, c = 13.414 (4) angstrom, and beta = 111.65 (2)-degrees. The structure was solved and refined using 4091 observed reflections measured on a SiemenB R3m/v diffractometer to a final R value of 2.66%. Crystals of 3 are monoclinic, space group P2(1)/c, with a = 13.980 (4) angstrom, b = 10.324 (2) angstrom, c = 13.146 (3) angstrom, beta = 115.18(2)-degrees, and Z = 2. On the basis of 4141 observed reflections, the structure was refined to R = 2.79. Crystals of 4 are monoclinic, space group P2(1)/c, with a = 7.642 (2) angstrom, b = 9.167 (2) angstrom, c = 16.493 (3) angstrom, beta = 93.05 (2)-degrees, and Z = 2. For 2905 observed reflections R was 2.56%. All three structure determinations were of high quality. Comparison of bond lengths between these complexes and related acetylides suggests that the trimethylsilyl-substituted bis(acetylides) or bis(diacetylides) have greater multiple-bond character in metal to acetylene sigma bonds than other acetylide derivatives.
引用
收藏
页码:4293 / 4300
页数:8
相关论文
共 43 条
[1]   THE X-RAY CRYSTAL-STRUCTURES OF [MO(C=CPH)(PH2PCH2CH2PPH2)(ETA-C7H7)] AND [MO(C=CPH)(PH2PCH2CH2PPH2)(ETA-C7H7)] [BF4] (C7H7 = CYCLOHEPTATRIENYL) - AN INVESTIGATION OF METAL-ALKYNYL BONDING [J].
BEDDOES, RL ;
BITCON, C ;
WHITELEY, MW .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1991, 402 (01) :85-96
[2]   NONLINEAR OPTICAL-PROPERTIES OF GROUP-10 METAL ALKYNYLS AND THEIR POLYMERS [J].
BLAU, WJ ;
BYRNE, HJ ;
CARDIN, DJ ;
DAVEY, AP .
JOURNAL OF MATERIALS CHEMISTRY, 1991, 1 (02) :245-249
[3]   FORMATION OF HYDRIDO- + CARBONYL COMPLEXES OF RUTHENIUM BY REACTION OF CERTAIN OF ITS COMPLEXES WITH ALCOHOLS [J].
CHATT, J ;
SHAW, BL ;
FIELD, AE .
JOURNAL OF THE CHEMICAL SOCIETY, 1964, (SEP) :3466-&
[4]   SYNTHESIS OF HYDRIDO-BIS(ACETYLIDE) COMPLEXES OF RHODIUM AND THE MOLECULAR-STRUCTURES OF MER-TRANS-[RH(PME3)3(H)(C=CPH)2] AND MER-TRANS-[(RH(DMPE)(H)(C=CSIME3)2)2(MU-ME2PCH2CH2PME2)] [J].
CHOW, P ;
ZARGARIAN, D ;
TAYLOR, NJ ;
MARDER, TB .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (20) :1545-1547
[5]   CRYSTAL AND MOLECULAR-STRUCTURE OF "1,8-BIS(TRIMETHYLSILYL)OCTATETRAYNE [J].
COLES, BF ;
HITCHCOCK, PB ;
WALTON, DRM .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1975, (05) :442-445
[6]   ELECTRICAL-CONDUCTIVITY OF FECL3-DOPED POLY(ALKYNYLSILANE)S [J].
CORRIU, RJP ;
DOUGLAS, WE ;
YANG, ZX ;
GARNIER, F ;
YASSAR, A .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1991, 417 (03) :C50-C52
[7]   SYNTHESIS OF POLY(ALKYNYLSILANES) HAVING VARIOUS AROMATIC-GROUPS IN THE BACKBONE [J].
CORRIU, RJP ;
DOUGLAS, WE ;
YANG, ZX .
JOURNAL OF POLYMER SCIENCE PART C-POLYMER LETTERS, 1990, 28 (13) :431-437
[8]  
CORRIU RJP, 1992, ORGANOMETALLICS, V11, P2057
[9]  
Cotton F. A., 1988, ADV INORG CHEM, P60
[10]   SYNTHESIS OF LINKED METAL ACETYLIDE COMPLEXES FOR NONLINEAR OPTICS [J].
DAVIES, SJ ;
JOHNSON, BFG ;
LEWIS, J ;
KHAN, MS .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1991, 401 (03) :C43-C45