CORE CONFORMATIONAL REARRANGEMENT ACCOMPANYING 2-CENTER, BIMETALLIC REDOX REACTIONS - CHEMICAL AND STRUCTURAL-PROPERTIES OF THE PYRAZOLYL-BRIDGED RHODIUM DIMERS [RH(ETA-5-C5ME5)CL(MU-PZ)]2 AND [RH(ETA-5-C5H5)(MU-PZ)]2

被引：21

作者：

BAILEY, JA ^{[1
]}

GRUNDY, SL ^{[1
]}

STOBART, SR ^{[1
]}

机构：

[1] UNIV VICTORIA,DEPT CHEM,VICTORIA V8W 2Y2,BC,CANADA

来源：

ORGANOMETALLICS | 1990年 / 9卷 / 02期

关键词：

D O I：

10.1021/om00116a038

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction between [Rh(η5-C5Me5)CI(μ-pz)]2 (5), which exhibits a ”chair” conformation for the core pyrazolyl- brldged bimetallic unit in the crystal with Rh2 separation 4.059 Å, and AgBF4 affords [Rh(η5-C5Me5)(μ-pz)2(μ-Cl)] 4 (6), in which the cation core exists in a “boat”h conformation with Rh centers 3.588 A apart; reduction (Zn/Cu) of 5 yields a purple product tentatively identified as [Rh(η5-C5Me5)(μ-pz)]2, the bright purple, reactive η5C5H5 analogue 9 of which has been synthesized from [Rh(η5-C5Me5)CI(μ-pz)]2 and shown by using single-crystal X-ray diffraction to possess a deeply folded (”boat”) geometry in which Rh-Rh = 2.657 (3) Å. © 1990, American Chemical Society. All rights reserved.

引用

收藏

页码：536 / 537

页数：2

相关论文

共 10 条

[1] PYRAZOLYL-BRIDGED IRIDIUM DIMERS .6. 2-FRAGMENT, 2-CENTER OXIDATIVE ADDITION OF HALOGENS AND METHYL HALIDES TO TRANS-BIS(TRIPHENYLPHOSPHINE)DICARBONYLBIS(MU-PYRAZOLYL)DIIRIDIUM(I) [J].

ATWOOD, JL ;

BEVERIDGE, KA ;

BUSHNELL, GW ;

DIXON, KR ;

EADIE, DT ;

STOBART, SR ;

ZAWOROTKO, MJ .

INORGANIC CHEMISTRY, 1984, 23 (24) :4050-4057

[2] BINUCLEAR OXIDATIVE ISOMERIZATION AS A MODEL FOR SURFACE-REACTIONS - INTRAMOLECULAR CHARACTER AND KINETIC PROFILE OF IODOMETHYLDI-IRIDIUM(II) - MU-METHYLENEDI-IRIDIUM(III) CONVERSION THAT FOLLOWS DI-IODOMETHANE ADDITION TO [IR(CO)(PPH3)(MU-PZ)]2 (HPZ = PYRAZOLE) [J].

BROST, RD ;

STOBART, SR .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (08) :498-500

[3] CO-OPERATIVITY EFFECTS BETWEEN ADJACENT METAL SITES - KINETICS OF METHYL-IODIDE ADDITION TO PYRAZOLYL-BRIDGED IRIDIUM DIMERS - ARGUMENT FOR A CONCERTED MECHANISM IN THE REVERSIBLE 2-FRAGMENT, 2-CENTER OXIDATIVE ADDITION TO THE CYCLO-OCTA-1,5-DIENE DI-IRIDIUM(I) COMPLEX [IR(COD)(MU-PZ)]2 [J].

BROST, RD ;

FJELDSTED, DOK ;

STOBART, SR .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (08) :488-490

[4] PYRAZOLYL-BRIDGED IRIDIUM DIMERS .2. CONTRASTING MODES OF 2-CENTER OXIDATIVE ADDITION TO A BIMETALLIC SYSTEM AND REDUCTIVE ACCESS TO THE STARTING COMPLEX - 3 KEY DIIRIDIUM STRUCTURES REPRESENTING SHORT NON-BONDING AND LONG AND SHORT BONDING METAL-METAL INTERACTIONS [J].

COLEMAN, AW ;

EADIE, DT ;

STOBART, SR ;

ZAWOROTKO, MJ ;

ATWOOD, JL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (03) :922-923

[5] MOLECULAR-STRUCTURE OF MU-PYRAZOLE-BIS(ETA5-CYCLOPENTADIENYL)TITANIUM(III), A DIMERIC TITANIUM(III) COMPOUND WITH A BRIDGING ORGANIC GROUP [J].

FIESELMANN, BF ;

STUCKY, GD .

INORGANIC CHEMISTRY, 1978, 17 (08) :2074-2077

[6]

FJELDSTED DOK, 1985, J AM CHEM SOC, V105, P8258

[7] STABILITY OF IODOALKYL DI-IRIDIUM(II) COMPLEXES - BRIDGE-FORMATION BY IODOMETHYL - MU-METHYLENE RING-CLOSURE AT A BIMETAL CENTER [J].

HARRISON, DG ;

STOBART, SR .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1986, (04) :285-286

[8] PENTAMETHYLCYCLOPENTADIENYLRHODIUM AND -IRIDIUM HALIDES .I. SYNTHESIS AND PROPERTIES [J].

KANG, JW ;

MOSELEY, K ;

MAITLIS, PM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1969, 91 (22) :5970-&

[9] DI(MU-PYRAZOLATE)BIS(PENTAMETHYLCYCLOPENTADIENYL)RHODIUM COMPLEXES - MOLECULAR-STRUCTURE OF [(RH(C5ME5)(PYRAZOLATE)]2(MU-PYRAZOLATE)2] [J].

ORO, LA ;

CARMONA, D ;

LAMATA, MP ;

FOCESFOCES, C ;

CANO, FH .

INORGANICA CHIMICA ACTA-ARTICLES AND LETTERS, 1985, 97 (01) :19-23

[10]

ORO LA, 1987, J CHEM SOC DA, P639