HETEROBINUCLEAR IRRH, RURH AND RUIR COMPLEXES WITH PYRAZOLATE BRIDGING LIGANDS - REACTIVITY TOWARDS CHELATING DIPHOSPHINES - CRYSTAL-STRUCTURE OF [(C5ME5)IR(MU-PZ)2(MU-CO)-IR(CO)(DPPEN)]BPH4.0.5MEOH [PZ = PYRAZOLATE, DPPEN = CIS-1,2-BIS(DIPHENYLPHOSPHINO)ETHYLENE]

被引:29
作者
CARMONA, D
FERRER, J
LAHOZ, FJ
ORO, LA
REYES, J
ESTEBAN, M
机构
[1] UNIV ZARAGOZA,DEPT QUIM INORGAN,CTR POLITECN SUPER INGN,E-50015 ZARAGOZA,SPAIN
[2] ESCUELA UNIV INGN TECN IND,DEPT QUIM INORGAN,E-50009 ZARAGOZA,SPAIN
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1991年 / 11期
关键词
D O I
10.1039/dt9910002811
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Complexes of general formula [LClM (mu-pz)2M'(cod)] 1-5 [L = C5Me5, M = Rh or lr; L = p-cymene, Me = Ru; M' = Rh or lr; pz = pyrazolate; cod = cycloocta-T,5-diene (not all possible combinations)] and [(MeC6H4Pr(i)-p)Ru(mu-pz)(mu-Cl)2Rh(cod)] 7 were prepared starting from mononuclear acetylacetonate and pyrazole or pyrazolate-containing moieties. Complexes 1-5 react with CO yielding derivatives [LClM(mu-pz)2M'(CO)2] 8-12. Complexes [(C5Me5)ClRh(mu-pz)2Rh(CO)2] 13 and [(MeC6H4Pr(i)-p)ClRu(mu-pz)2lr(CO)2] 12 react with NaX to give [(C5Me5)XRh(mu-pz)2Rh(CO)2] (X = 1, 14; or N3, 15) and [(MeC6H4Pr(i)-p) activated Ru(mu-pz)2lrX(CO)2] (X = Br, 16; or l, 17. The dicarbonyl compound 10 and [(MeC6H4Pr(i)-p)ClRu(mu-pz)2M'(CO)2] (M' = Rh, 11; or lr, 12) react with diphosphines (L-L) or 1,2-bis(diphenylarsino)ethane (dpae) and NaBPh4 or AgBF4 affording cationic complexes [LM(mu-pz)2(mu-CO)M'(L-L)]A 23-31 [L-L = bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)-ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, cis-1,2-bis-(diphenylphosphino)ethylene (dppen) or dpae; A = BPh4 or BF4 (not all possible combinations)]. In this reaction intermediates [LM(mu-pz)2(mu-CO)M'(CO)(L-L)]A have been isolated in some cases. The crystal structure of one of these [(C5Me5)Ir(mu-pz)2(mu-CO)Ir(CO)(dppen)]BPh4.0.5MeOH 19 has been determined by X-ray diffraction methods. Crystals are monoclinic, space group P2(1)/c, a = 15.996(2), b = 22.199(4), c = 18.874(3) angstrom, beta = 115.04(1)-degrees and Z = 4. The complex cation consists of two iridium atoms bridged by two pyrazolates and one ketonic carbonyl group. An eta-5-C5Me5 ligand, a chelate dppen and a terminal CO group complete the co-ordination spheres of the iridium atoms, which are separated by 3.440(5) angstrom.
引用
收藏
页码:2811 / 2820
页数:10
相关论文
共 36 条
[1]  
[Anonymous], 1974, INT TABLES XRAY CRYS, VIV
[2]   X-RAY CRYSTAL-STRUCTURE OF (ETA-5-PENTAMETHYLCYCLOPENTADIENYL)(ETA-3-1,3-DIMETHYLALLYL)CHLORORHODIUM-LOCALIZED DI-PI-OLEFIN-SIGMA BONDING OF CYCLOPENTADIENYL [J].
BATSANOV, AS ;
STRUCHKOV, YT .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1984, 265 (03) :305-310
[3]   SYNTHESIS AND SPECTROSCOPIC CHARACTERIZATION OF DINUCLEAR MONO(MU-HYDRIDO) ARENE COMPLEXES OF DIVALENT RUTHENIUM [J].
BENNETT, MA ;
ENNETT, JP .
ORGANOMETALLICS, 1984, 3 (09) :1365-1374
[4]   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
[5]   PROBLEMS IN THE ASSIGNMENT OF BONDING MODE OF BRIDGING CARBONYL GROUPS FROM THE CARBONYL STRETCHING FREQUENCY - MOLECULAR-STRUCTURE OF BIS-MU-[BIS(DIPHENYLARSINO)METHANE]-MU-CARBONYL-BIS-[CHLOROPLATINUM(II)] [J].
BROWN, MP ;
KEITH, AN ;
MANOJLOVICMUIR, L ;
MUIR, KW ;
PUDDEPHATT, RJ ;
SEDDON, KR .
INORGANICA CHIMICA ACTA, 1979, 34 (01) :L223-L224
[6]   SYNTHESIS, X-RAY STRUCTURE, AND NUCLEAR-MAGNETIC-RESONANCE (H-1 AND C-13) STUDIES OF RUTHENIUM(II) COMPLEXES CONTAINING PYRAZOLYL LIGANDS [J].
CARMONA, D ;
FERRER, J ;
ORO, LA ;
APREDA, MC ;
FOCESFOCES, C ;
CANO, FH ;
ELGUERO, J ;
JIMENO, ML .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1990, (04) :1463-1476
[7]   SYNTHESIS AND CHARACTERIZATION OF THE ALKOXYCARBONYL COMPLEXES [(C5ME5)M-(MU-PZ)(MU-I)2RHI(CO2R)(CO)] (M = RH, R = ME OR ET, M = IR, R = ME, PZ = PYRAZOLATE) - MOLECULAR-STRUCTURE OF [(C5ME5)IR(MU-PZ)(MU-I)2RHI(CO2ME)(CO)] [J].
CARMONA, D ;
LAHOZ, FJ ;
ORO, LA ;
REYES, J ;
LAMATA, MP .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1990, (11) :3551-3555
[8]   REACTIVITY OF BINUCLEAR PYRAZOLATE-BRIDGED RHODIUM COMPLEXES WITH ISOCYANIDES - MOLECULAR-STRUCTURE OF [RH2(MU-PZ)L2(CNBUT)2-(MU-PH2PCH2PPH2)2]BF4 (PZ = PYRAZOLATE) [J].
CARMONA, D ;
ORO, LA ;
PEREZ, PL ;
TIRIPICCHIO, A ;
TIRIPICCHIOCAMELLINI, M .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1989, (08) :1427-1433
[9]  
CARMONA D, IN PRESS ANGEW CHEM
[10]   OLEFIN CO-ORDINATION COMPOUNDS .16. DIENE COMPLEXES OF RHODIUM(I) [J].
CHATT, J ;
VENANZI, LM .
JOURNAL OF THE CHEMICAL SOCIETY, 1957, (DEC) :4735-4741