SYNTHESIS, STRUCTURE AND REACTIVITY OF DINUCLEAR HYDRIDO-BRIDGED OSMIUM COMPLEXES WITH OS-OS DOUBLE AND TRIPLE BOND

被引:18
作者
SCHULZ, M [1 ]
STAHL, S [1 ]
WERNER, H [1 ]
机构
[1] UNIV WURZBURG,INST ANORGAN CHEM,W-8700 WURZBURG,GERMANY
关键词
D O I
10.1016/0022-328X(90)87250-H
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The dinuclear mesitylene osmium complexes [(Mes)2Os2(μ-H)3]X (2a,b) and [(Mes)OsH(μ-H)]2 (3) are prepared from [(Mes)OsCl2]n (1) and NaBH4. The complex 2a (X = Cl) and its corresponding BF4 salt 2c can also be obtained from the reaction of 3 with HCl or HBF4, respectively. The structures of 2a and 3 have been determined by single-crystal X-ray diffraction studies. The cation of 2a contains two equivalent (Mes)Os fragments linked by a rather short OsOs bond (247.41(2) pm) and three bridging hydride ligands. The midpoints of the six-membered rings together with the two osmium atoms form a linear unit. The metal-metal distance in compound 3 (267.34(6) pm) is significantly longer than that in the cation of 2a and corresponds to an OsOs double bond. The trans arrangement of the mesitylene rings with regard to the metal-metal bond axis indicates that two of the hydride ligands in 3 are terminal and two are bridging. An equilibrium between the cis and trans isomers of 3 probably exists in CD2Cl2 solution. Treatment of [(Mes)OsCl2(PMe3)] (4) with NaBH4 or LiAlH4 affords the dihydrido complex [(Mes)OsH2(PMe3)] (5) which is also one of the products of the reaction of 3 with PMe3. Compound 5 is photoreactive and on UV irradiation in benzene gives the hydrido phenyl complex [(Mes)OsH(C6H5)PMe3]. © 1990.
引用
收藏
页码:469 / 479
页数:11
相关论文
共 24 条
[1]   QUADRUPLY HYDROGEN-BRIDGED METAL-METAL BOND - NEUTRON-DIFFRACTION ANALYSIS OF H8RE2(PET+PH)4 [J].
BAU, R ;
CARROLL, WE ;
TELLER, RG ;
KOETZLE, TF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (11) :3872-3874
[2]   PROTONATION OF DICYCLOPENTADIENE COMPLEXES OF RUTHENIUM(0), OSMIUM(0), RHODIUM(I), AND IRIDIUM(I) - SINGLE-CRYSTAL X-RAY STUDY OF [OS(2,3,5-ETA-C10H13)(ETA-C6H3ME3-1,3,5)]PF6, A COMPLEX CONTAINING AN OS-H-C INTERACTION [J].
BENNETT, MA ;
MCMAHON, IJ ;
PELLING, S ;
ROBERTSON, GB ;
WICKRAMASINGHE, WA .
ORGANOMETALLICS, 1985, 4 (04) :754-761
[3]  
BROACH RW, 1979, INORG CHEM, V18, P314, DOI 10.1021/ic50192a021
[4]   THE SYNTHESIS OF DI-NUCLEAR AND TETRA-NUCLEAR PARA-CYMENE-OSMIUM HYDRIDE COMPLEXES - CHARACTERIZATION BY H-1 (OS-187) REVERSE INEPT TWO-DIMENSIONAL NUCLEAR MAGNETIC-RESONANCE SPECTROSCOPY [J].
CABEZA, JA ;
MANN, BE ;
MAITLIS, PM ;
BREVARD, C .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1988, (03) :629-634
[5]   SYNTHESIS AND CHARACTERIZATION OF AN UNUSUAL ASYMMETRIC DIOSMIUM COMPLEX, OS2CL3(PHNPY)3 [J].
CHAKRAVARTY, AR ;
COTTON, FA ;
TOCHER, DA .
INORGANIC CHEMISTRY, 1984, 23 (26) :4693-4697
[6]   STRUCTURAL STUDIES OF POLYNUCLEAR OSMIUM CARBONYL HYDRIDES .5. CRYSTAL-STRUCTURE AND MOLECULAR-GEOMETRY OF DI-MU-HYDRIDO-DECACARBONYLTRIOSMIUM, (MU-H)2OS3(CO)10 [J].
CHURCHILL, MR ;
HOLLANDER, FJ ;
HUTCHINSON, JP .
INORGANIC CHEMISTRY, 1977, 16 (11) :2697-2700
[7]  
Cotton F.A, 1982, MULTIPLE BONDS METAL
[8]  
COTTON FA, 1985, STRUCT BOND, V62, P1
[9]   ADDITION-REACTIONS OF A POLYNUCLEAR OSMIUM HYDRIDO COMPOUND LEADING TO ASSOCIATIVE CARBONYL SUBSTITUTION AND CATALYTIC ALKENE ISOMERIZATION [J].
DEEMING, AJ ;
HASSO, S .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1976, 114 (03) :313-324
[10]   MULTIPLY BONDED OCTAHALODIOSMATE(III) ANIONS .3. SYNTHESIS AND CHARACTERIZATION OF THE OCTAHALODIOSMATE(III) ANIONS (OS2CL8)2-, (OS2BR8)2- - CRYSTAL-STRUCTURE DETERMINATIONS OF 2 FORMS OF (BIS(TRIPHENYLPHOSPHINE)NITROGEN(1+))2OS2CL8 [J].
FANWICK, PE ;
TETRICK, SM ;
WALTON, RA .
INORGANIC CHEMISTRY, 1986, 25 (25) :4546-4552