CARBON-CARBON BOND-CLEAVAGE BY OSMIUM CLUSTERS - RING-OPENING OF A CYCLOBUTENYL LIGAND BY A TRIOSMIUM CLUSTERS

被引:8
作者
ADAMS, RD
QU, XS
机构
[1] Department of Chemistry and Biochemistry, University of South Carolina, Columbia
关键词
D O I
10.1021/om00009a019
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction of 1-iodo-2-methylcyclobutene with the triosmium cluster complex OS3(CO)(10)-(NCMe)(2) has yielded four new osmium cluster compounds: Os-2(CO)(6)(mu-I)[mu-CC(Me)CH2CH2], 1 (5% yield), Os-3(CO)(9)(mu-I)[mu(3)-CC(Me)CH2CH2], 2 (8% yield), Os-3(CO)(9)(mu-I)[mu(3)-CC(Me)CH2-CH2], 3 (16% yield), and Os-3(CO)(10)(mu-I)[mu-CC(Me)CH2CH2], 4 (33% yield). Compounds 1-3 were characterized by single-crystal X-ray diffraction analysis. Compounds 1 and 4 contain a sigma,pi-coordinated 2-methylcyclobutenyl ligand. Compounds 2 and 3 are isomers. Both contain open triosmium clusters with a metalated acyclic sigma,pi-coordinated bridging alkenylidene ligand formed by the cleavage of one of the carbon-carbon bonds of the cyclobutenyl ring. An iodo ligand bridges one of the two metal-metal bonds in 2 and the nonbonded Os-Os pair of metal atoms in 3. Compound 2 is an intermediate to 3 and is converted to 3 in 90% yield in solution at 25 degrees C in 48 h. From the structure of 2 it can be inferred that the C-C bond cleavage process involves a direct oxidative addition of the C-CH2 carbon-carbon sigma-bond of the sigma,pi-coordinated bridging cyclobutenyl ligand in 4 adjacent to the pi-coordinated C-C double bond and occurs at the same metal atom. Crystal data for 1: space group = P2(1)/n, a = 8.376(2) Angstrom, b = 13.925(2) Angstrom, c = 13.138(3) Angstrom, beta = 102.32(1)degrees, Z = 4, 1719 reflections, R = 0.033. For 2: space group = P $($) over bar$$ 1, a = 9.146(2) Angstrom, b = 14.618(3) Angstrom, c = 8.528(2) Angstrom, alpha = 94.49(2)degrees, beta = 116.38(1)degrees, gamma = 81.94(2)degrees, Z = 2, 2246 reflections, R = 0.025. For 3: space group = P $($) over bar$$ 1, a = 13.900(3) Angstrom, b = 18.022(6) Angstrom, c = 12.896(2) Angstrom, alpha = 94.82(2)degrees, beta = 109.44(1)degrees, gamma = 90.17(2)degrees, Z = 6, 3941 reflections, R = 0.045.
引用
收藏
页码:4167 / 4172
页数:6
相关论文
共 18 条
[1]   CYCLOBUTYNE LIGANDS .4. RUTHENIUM CARBONYL CLUSTERS CONTAINING SUBSTITUTED CYCLOBUTYNE LIGANDS AND THE 1ST EXAMPLE OF A QUADRUPLY BRIDGING CYCLOBUTYNE LIGAND [J].
ADAMS, RD ;
QU, XS ;
WU, WG .
ORGANOMETALLICS, 1994, 13 (04) :1272-1280
[2]   CYCLOBUTYNE LIGANDS .1. SYNTHESIS AND REACTIVITY OF A CYCLOBUTYNE LIGAND IN A TRIOSMIUM COMPLEX, INCLUDING A STRUCTURAL CHARACTERIZATION OF THE 1ST CYCLOBUTYNE LIGAND IN THE COMPLEX OS3(CO)9(MU-3-ETA-2-C2CH2CH2)(MU-SPH)(MU-H) [J].
ADAMS, RD ;
CHEN, G ;
QU, XS ;
WU, WG ;
YAMAMOTO, JH .
ORGANOMETALLICS, 1993, 12 (08) :3029-3035
[3]   CYCLOBUTYNE LIGANDS .5. C-H BOND-CLEAVAGE VERSUS RING-OPENING OF ALPHA,PI-COORDINATED CYCLOBUTENYL LIGANDS [J].
ADAMS, RD ;
CHEN, LF ;
QU, XS .
ORGANOMETALLICS, 1994, 13 (05) :1992-1998
[4]   CYCLOBUTYNE - THE LIGAND - THE SYNTHESIS AND MOLECULAR-STRUCTURE OF OS3(CO)9(MU-3-ETA-2-C2CH2CH2)(MU-SPH)(MU-H) [J].
ADAMS, RD ;
CHEN, G ;
QU, XS ;
WU, WG ;
YAMAMOTO, JH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (27) :10977-10978
[5]   CYCLOBUTYNE LIGANDS .3. SYNTHESIS AND CHARACTERIZATION OF A DISUBSTITUTED CYCLOBUTYNE LIGAND IN THE TRIOSMIUM COMPLEX OS3(CO)9[(MU(3)-ETA(2)-C2CH2C(ME)TBU)]MU(3)-S) [J].
ADAMS, RD ;
QU, XS ;
WU, WG .
ORGANOMETALLICS, 1993, 12 (10) :4117-4122
[6]   INTRAMOLECULAR NUCLEOPHILIC-ATTACK AT THE ALPHA-CARBON ATOM OF A MU-3-ALKYNYL LIGAND IN A TRIOSMIUM CLUSTER [J].
AIME, S ;
DEEMING, AJ .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1983, (08) :1807-1809
[7]   REACTIONS AND PROPERTIES OF SOME TRIMETHYLENEPLATINUM(IV) COMPLEXES .9. CHEMISTRY OF PLATINACYCLOBUTANES DERIVED FROM 1,2-DISUBSTITUTED CYCLOPROPANES [J].
ALESSA, RJ ;
PUDDEPHATT, RJ ;
THOMPSON, PJ ;
TIPPER, CFH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (25) :7546-7553
[8]   DIMETHYLALLENEDIYL AS AN ETA-1,ETA-2-BRIDGING LIGAND IN A DIZIRCONOCENE COMPLEX [J].
BINGER, P ;
LANGHAUSER, F ;
GABOR, B ;
MYNOTT, R ;
HERRMANN, AT ;
KRUGER, C .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1992, (06) :505-506
[9]   TRANSITION-METAL CATALYZED REARRANGEMENTS OF SMALL RING ORGANIC-MOLECULES [J].
BISHOP, KC .
CHEMICAL REVIEWS, 1976, 76 (04) :461-486
[10]  
BOARDMAN LD, 1984, J AM CHEM SOC, V106, P6105, DOI 10.1021/ja00332a072