Dimethylsulfoxide as a ligand for RhI and IrI complexes -: Isolation, structure, and reactivity towards X-H bonds (X = H, OH, OCH3)

被引:56
作者
Dorta, R
Rozenberg, H
Shimon, LJW
Milstein, D [1 ]
机构
[1] Weizmann Inst Sci, Dept Organ Chem, IL-76100 Rehovot, Israel
[2] Weizmann Inst Sci, Unit Chem Res Support, IL-76100 Rehovot, Israel
关键词
iridium; O ligands; oxidative addition; rhodium; S ligands;
D O I
10.1002/chem.200305144
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Novel neutral and cationic Rh-I and Ir-I complexes that contain only DMSO molecules as dative ligands with S-, O-, and bridging S,O-binding modes were isolated and characterized. The neutral derivatives [RhCl(DMSO)(3)] (1) and [IrCl(DMSO)(3)] (2) were synthesized from the dimeric precursors [M2Cl2(coe)(4)] (M=Rh, Ir; COE=cyclooctene). The dimeric Ir-I compound [Ir,Cl,(DMSO)41 (3) was obtained from 2. The first example of a square-planar complex with a bidentate S,O-bridging DMSO ligand, [(coe)(DMSO)Rh-(mu-Cl)(mu-DMSO)RhCl(DMSO)] (4), was obtained by treating [Rh2Cl2(coe)(4)] with three equivalents of DMSO. The mixed DMSO-olefin complex [IrCl(cod)(DMSO)] (5, COD=cyclooctadiene) was generated from [lr(2)Cl(2)(cod)(2)]. Substitution reactions of these neutral systems afforded the complexes [RhCl(py)(DMSO)(2)] (6), [IrCl(py)(DMSO)(2)] (7), [IrCl(iPr(3)P)(DMSO)(2)] (8), [RhCl(dmbpy)(DMSO)] (9, dmbpy = 4,4'-dimethyl-2,2'-bipyridine), and [lrCl(dmbpy)(DMSO)] (10). The cationic O-bound complex [Rh(cod)(DMSO)(2)]BF4 (11) was synthesized from [Rh(cod)(2)]BF4. Treatment of the cationic complexes [M(coe)(2)(O=C-Me-2)(2)]PF6 (M=Rh, Ir) with DMSO gave the mixed S- and O-bound DMSO complexes [M(DMSO)(2)(DMSO)(2)]PF6 (Rh=12; Ir=in situ characterization). Substitution of the O-bound DMSO ligands with dmbpy or pyridine resulted in the isolation of [Rh(dmbpy)(DMSO)(2)]PF6 (13) and [Ir(py)(2)(DMSO)(2)]PF6 (14). Oxidative addition of hydrogen to [IrCl(DMSO)(3)] (2) gave the kinetic product fac-[Ir(H)(2)Cl(DMSO)(3)] (15) which was then easily converted. to the more thermodynamically stable product mer-[Ir(H)(2)Cl(DMSO)(3)] (16). Oxidative addition of water to both neutral and cationic Ir-I DMSO complexes gave the corresponding hydrido-hydroxo addition products syn-(DMSO)(2)HIr(mu-OH)(2)- (mu-Cl)IrH(DMSO)(2)][IrCl2(DMSO)(2)] (17) and anti-[(DMSO)(2)(DMSO)HIr(mu-OH)(2)- IrH(DMSO)(2)(DMSO)][PF6](2) (18). The cationic [Ir(DMSO)(2)(DMSO)(2)]PF6 complex (formed in situ from [Ir(coe)(2)(O=CMe2)(2)]PF6) also reacts with methanol to give the hydrido-alkoxo complex syn[(DMSO)(2)HIr(mu-OCH3)(3)IrH(DMSO)(2)]- PF6 (19). Complexes 1, 2, 4, 5, 11, 12, 14, 17, 18, and 19 were characterized by crystallography.
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页码:5237 / 5249
页数:13
相关论文
共 63 条
[1]   STRUCTURE OF THE PRECURSOR OF AN IRIDIUM-CONTAINING HYDROGENATION CATALYST [J].
ABBASSIOUN, MS ;
HITCHCOCK, PB ;
CHALONER, PA .
ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1989, 45 :953-954
[2]   A NEW LINKAGE ISOMER OF RHCL3(DMSO)(3) - PHOTOCHEMICAL-SYNTHESIS, CRYSTAL-STRUCTURE, AND REACTIVITY OF MER,TRANS-RHCL3(DMSO)(2)(DMSO) [J].
ALESSIO, E ;
FALESCHINI, P ;
SANTI, ASO ;
MESTRONI, G ;
CALLIGARIS, M .
INORGANIC CHEMISTRY, 1993, 32 (25) :5756-5761
[3]  
[Anonymous], INORG SYNTH
[4]   CRYSTAL AND MOLECULAR-STRUCTURE OF ORANGE AND RED ALLOTROPES OF CHLOROTRIS(TRIPHENYLPHOSPHINE)RHODIUM(I) [J].
BENNETT, MJ ;
DONALDSON, PB .
INORGANIC CHEMISTRY, 1977, 16 (03) :655-660
[5]   Oxidative addition of water and aliphatic alcohols by IrCl(trialkylphosphine)3 [J].
Blum, O ;
Milstein, D .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (38) :11456-11467
[6]  
BLUM O, 1995, ANGEW CHEM INT EDIT, V34, P229, DOI 10.1002/anie.199502291
[7]  
BLUM O, 1995, ANGEW CHEM, V107, P210
[8]   SYNTHESIS OF MONOMERIC RUTHENIUM HYDROXO COMPLEXES (PME3)4RU(R)(OH) (R = H, ME) AND A UNIQUE DIMERIC RUTHENIUM HYDROXO WATER COMPLEX [TRANS-RU(H)(OH)(DMPE)2.H2O]2 [J].
BURN, MJ ;
FICKES, MG ;
HARTWIG, JF ;
HOLLANDER, FJ ;
BERGMAN, RG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (13) :5875-5876
[9]   STRUCTURE OF TRANS-DICHLOROTETRAKIS(DIMETHYL SULFOXIDE)RHODIUM(III) TETRAFLUOROBORATE [J].
CALLIGARIS, M ;
FALESCHINI, P ;
ALESSIO, E .
ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1991, 47 :747-750
[10]   Structure and bonding in metal sulfoxide complexes [J].
Calligaris, M ;
Carugo, O .
COORDINATION CHEMISTRY REVIEWS, 1996, 153 :83-154