DINUCLEAR ISOCYANIDE DERIVATIVES OF HW2(CO)9(NO) - SYNTHESIS, STRUCTURE, AND MECHANISTIC STUDIES

被引:5
作者
LIN, JT [1 ]
CHEN, CC [1 ]
HUANG, PS [1 ]
HONG, FE [1 ]
WEN, YS [1 ]
机构
[1] NATL CHUNGHSING UNIV,DEPT CHEM,TAICHUNG,TAIWAN
关键词
D O I
10.1021/om00034a038
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reactions of HW2(CO)9(NO) and HW2(CO)7(THF)2(NO) with excess RNC (R = Me, (t)Bu, PhCH2, (i)Pr) yields a yellow complex HW2(CO)7(RNC)2(NOax) (ax = axial) and its isomeric reddish complex HW2(CO)7(RNC)2(NOeq) (eq = equatorial). Both bent-staggered and bent-eclipsed conformations are found to exist in these isomers. Treatment of complexes HW2(CO)9(NO), HW2(CO)8(PPh3)(NO), HW2(CO)7(MeNC)2(NOax), and HW2(CO)7(MeNC)2(NOeq) with Ph3P=NR (R = (i)Pr, (n)Pr, Ph, (t)Bu) yields HW2(CO)8(RNC)(NOax) (R = (i)Pr, Ph, (t)Bu), HW2(CO)7(RNC)2(NOax) (R = (i)Pr, Ph), HW2(CO)7(PPh3)(nPrNC)(NOax), HW2(CO)6(PPh3)(nPrNC)2(NOax), and HW2(CO)6(MeNC)2(nPrNC)(NOeq). There is no rearrangement, which is found in the reaction of HW2(CO)9(NO) with RNC, of ligands during the conversion of coordinated CO ligands to RNC by Ph3PNR in these reactions. Electronic and steric influences on the sequential conversion of CO to RNC are supported by crystal structures determinations of several new complexes. Crystal data for HW2(CO)8(PhNC)(NOax): C15H6N2O9W2; P2(1)/c (monoclinic); a = 10.802(2), b = 11.705(1), c = 16.695(2) angstrom; beta = 108.67(1)degrees; Z = 4; R = 0.031, R(w) = 0.032. HW2(CO)6(PhNC)(nPrNC)2(NOax): C21H20N4O7W2; P1 (triclinic); a = 8.718(1), b = 11.135(2); c = 13.832(1) angstrom; alpha = 92.24(1), beta = 79.58(1), gamma = 91.53(1)degrees; Z = 2; R = 0.031, R(w) = 0.032. HW2(CO)6(MeNC)2(nPrNC)(NOeq): C14H14N4O7W2; P1 (triclinic); a = 10.140(2); b = 10.147(2); c = 11.346(2) angstrom; alpha = 84.34(2), beta = 112.86(2), gamma = 100.92(1)degrees; Z = 2; R = 0.033, R(w) = 0.037.
引用
收藏
页码:4016 / 4024
页数:9
相关论文
共 40 条
[1]   NOVEL DEOXYGENATION OF A CARBONYL GROUP OF IRON PENTACARBONYL [J].
ALPER, H ;
PARTIS, RA .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1972, 35 (01) :C40-&
[2]   CARBAMOYL AND ALKOXYCARBONYL COMPLEXES OF TRANSITION-METALS [J].
ANGELICI, RJ .
ACCOUNTS OF CHEMICAL RESEARCH, 1972, 5 (10) :335-&
[3]  
[Anonymous], 1974, INT TABLES XRAY CRYS, VIV
[4]  
CHEN LC, 1992, J ORGANOMET CHEM, V425, P99
[5]   STUDIES USING (N-BU)3P=O AS A CARBON-MONOXIDE LABILIZING LIGAND IN THE SYNTHESIS OF METAL-CARBONYL-COMPLEXES HIGHLY ENRICHED IN (CO)-C-13 [J].
DARENSBOURG, DJ ;
DARENSBOURG, MY ;
WALKER, N .
INORGANIC CHEMISTRY, 1981, 20 (06) :1918-1921
[6]   SYNTHESIS OF METAL-CARBONYL-COMPLEXES HIGHLY ENRICHED IN C-13 - UTILIZATION OF THE CO-LABILIZING ABILITY OF (N-BU)3P=O [J].
DARENSBOURG, DJ ;
WALKER, N ;
DARENSBOURG, MY .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (03) :1213-1214
[7]   REACTIONS OF TRANSITION METAL CARBONYLS WITH ORGANOLITHIUM COMPOUNDS .2. PREDICTION OF NUCLEOPHILIC ATTACK AT CARBON AND RESULTING STEREOCHEMISTRY [J].
DARENSBOURG, DJ ;
DARENSBOURG, MY .
INORGANIC CHEMISTRY, 1970, 9 (07) :1691-+
[8]  
DARENSBOURG DJ, 1982, ADV ORGANOMET CHEM, V21, P113
[9]   BINUCLEAR MOLYBDENUM CARBONYLS BRIDGED BOTH BY HYDRIDE AND BY BIDENTATE PHOSPHINE-LIGANDS - CRYSTAL AND MOLECULAR-STRUCTURES OF SALTS OF (MU-H)(MU-PH2P(CH2)NPPH2)MO2(CO)8-(N=1-4) AND THEIR REACTIONS WITH ACIDS [J].
DARENSBOURG, MY ;
ELMEHDAWI, R ;
DELORD, TJ ;
FRONCZEK, FR ;
WATKINS, SF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (09) :2583-2591
[10]  
Fischer, 1970, PURE APPL CHEM, V24, P407