Diazo complexes of rhenium:: Preparations and crystal structures of the bis(dinitrogen), [Re(N2)2{PPh(OEt)2}4][BPh4] and methyldiazenido [ReCl(CH3N2)(CH3NHNH2){PPh(OEt)2}3][BPh4] derivatives

被引:31
作者
Albertin, G
Antoniutti, S
Bacchi, A
Bordignon, E
Miani, F
Pelizzi, G
机构
[1] Univ Venice, Dipartimento Chim, I-30123 Venice, Italy
[2] Univ Parma, Ctr Strutturist Diffrattometr, CNR, Dipartimento Chim Gen & Inorgan, I-43100 Parma, Italy
关键词
D O I
10.1021/ic990970r
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Depending on experimental conditions and the nature of the hydrazine, the reactions of ReCl3P3 [P = PPh(OEt)(2)] with RNHNH2 (R = H, CH3, Bu-t) afford the bis(dinitrogen) [Re(N-2)(2)P-4](+) (2(+)), dinitrogen ReClN2P4 (3), and methyldiazenido [ReCl(CH3N2)(CH3NHNH2)P-3](+) (1(+)) derivatives. In contrast, reactions of ReCl3P3 [P = PPh(OEt)(2), PPh2OEt] with arylhydrazines ArNHNH2 (Ar = Ph, p-tolyl) give the aryldiazenido cations [ReCl(ArN2)(ArNHNH2)P-3](+) (4(+)) and [ReCl(ArN2)P-4](+) (7(+)) and the bis(aryldiazenido) cations [Re(ArN2)(2)P-3](+) (5(+), 6(+)). These complexes were characterized spectroscopically (IR; H-1 and P-31 NMR), and the BPh4 complexes 1, 2, and 7 were characterized crystallographically. The methyldiazenido derivative [ReCl(CH3N2)(CH3NHNH2){PPh(OEt)(2)}(3)][BPh4] (1) crystallizes in space group P (1) over bar: with a = 15.396(5) Angstrom, b = 16.986(5) Angstrom, c = 11.560(5) Angstrom, alpha = 93.96(5)degrees, beta = 93.99(5)degrees, gamma = 93.09(5)degrees, and Z = 2 and contains a singly bent CH3N2, group bonded to an octahedral central metal. One methylhydrazine ligand, one Cl- trans to the CH3N2, and three PPh(OEt)(2) ligands complete the coordination. The complex [Re(N-2)(2){PPh(OEt)(2)}(4)][BPh4] (2) crystallizes in space group Pbaa with a = 23.008(5) Angstrom, b = 23.367(5) Angstrom, c = 12.863(3) Angstrom, and Z = 4. The structure displays octahedral coordination with two end-on N-2 ligands in mutually trans positions. [ReCl(PhN2){PPh(OEt)(2)}(4)][BPh4] (7) crystallizes in space group P2(1)/n with a = 19.613(5) Angstrom, b = 20.101(5) Angstrom, c = 19.918(5) Angstrom, beta = 115.12(2)degrees, and Z = 4. The structure shows a singly bent phenyldiazenido group trans to the Cl- ligand in an octahedral environment. The dinitrogen complex ReClN2P4 (3) reacts with CF3SO3CH3 to give the unstable methyldiazenido derivative [ReCl(CH3N2)P-4][BPh4]. Reaction of the methylhydrazine complex [ReCl(CH3N2)(CH3NHNH2)P-3][BPh4] (1) with Pb(OAc)(4) at -30 degrees C results in selective oxidation of the hydrazine, affording the corresponding methyldiazene derivative [ReCl(CH3N= NH)(CH3N2)P-3][BPh4] (8). In contrast, treatment with Pb(OAc)(4) of the related arylhydrazines [ReCl(ArN2)(ArNHNH2)P-3][BPh4] (4) [P = PPh(OEt)(2)] gives the bis(aryldiazenido) complexes [Re(ArN2)(2)P-3][BPh4] (5). Possible protonation reactions of Bronsted acids HX with all diazenides, 1, 4, 5, 6, and 8, were investigated and found to proceed only in the cases of the bis(aryldiazenido) complexes 5 and 6, affording, with HCl, the octahedral [ReCl(ArN=NH)(ArN2)P-3][BPh4] or [ReCl{Ar(H)NN}(ArN2)P-3][BPh4] (10) (Ar = Ph; P = PPh2OEt) derivative.
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页码:3283 / 3293
页数:11
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共 112 条
[91]   THE SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF [RECL2(PPH3)2(NNHCOPH)(NHNHCOPH)].1/2ET2O, A COMPLEX EXHIBITING LINEAR HYDRAZIDO(2-) LIGATION AND END-ON HYDRAZIDO(1-) LIGATION [J].
NICHOLSON, T ;
ZUBIETA, J .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1985, (06) :367-368
[92]   A model for protonation of dinitrogen by nitrogenase: Protonation of coordinated dinitrogen on tungsten with hydrosulfido-bridged dinuclear complexes [J].
Nishibayashi, Y ;
Iwai, S ;
Hidai, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (40) :10559-10560
[93]   Heterodinuclear uranium/molybdenum dinitrogen complexes [J].
Odom, AL ;
Arnold, PL ;
Cummins, CC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (23) :5836-5837
[94]   ''Fixation'' of dinitrogen by molybdenum and the formation of a trigonal planar iron-tris[molybdenum(dinitrogen)] complex [J].
ODonoghue, MB ;
Zanetti, NC ;
Davis, WM ;
Schrock, RR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (11) :2753-2754
[95]   A VERSATILE SYNTHON FOR THE PREPARATION OF CHIRAL RHENIUM(I)-AMINE COMPLEXES AND SYNTHESIS OF AN ETA(2)-BENZALDEHYDE SPECIES [J].
ORTH, SD ;
BARRERA, J ;
SABAT, M ;
HARMAN, WD .
INORGANIC CHEMISTRY, 1994, 33 (14) :3026-3027
[96]   PREPARATION OF ISOCYANIDE AND MIXED DINITROGEN ISOCYANIDE COMPLEXES OF RHENIUM(I) FROM REACTIONS OF TRANS-[RECL(N2)(PME2PH)4], MER-[RE-(S2PPH2)(N2)(PME2PH)3], OR MER-[RE(S2CNET2)(N2)(PME2PH)3] WITH METHYL ISOCYANIDE - CRYSTAL-STRUCTURE OF MER-[RE(S2PPH2)(N2)(CNME)(PME2PH)3] [J].
POMBEIRO, AJL ;
HITCHCOCK, PB ;
RICHARDS, RL .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1987, (02) :319-325
[97]   PHOSPHORUS-CONTAINING MONOMERS .1. SYNTHESIS OF VINYL PHOSPHINES, OXIDES, SULFIDES, AND PHOSPHONIUM COMPOUNDS [J].
RABINOWITZ, R ;
PELLON, J .
JOURNAL OF ORGANIC CHEMISTRY, 1961, 26 (11) :4623-&
[98]   TRANS-[NA(THF)][V(N2)2(PH2PCH2CH2PPH2)2] - STRUCTURAL CHARACTERIZATION OF A DINITROGENVANADIUM COMPLEX, A FUNCTIONAL-MODEL FOR VANADIUMNITROGENASE [J].
REHDER, D ;
WOITHA, C ;
PRIEBSCH, W ;
GAILUS, H .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1992, (04) :364-365
[99]   Reactions of small molecules at transition metal sites: Studies relevant to nitrogenase, an organometallic enzyme [J].
Richards, RL .
COORDINATION CHEMISTRY REVIEWS, 1996, 154 :83-97
[100]   INVESTIGATION OF THE ELECTROCHEMICAL REDUCTION OF [CP-ASTERISK-RE(CO)2(P-N2C6H4OME)][BF4] BY SCANNING ELECTROCHEMICAL MICROSCOPY [J].
RICHARDS, TC ;
BARD, AJ ;
CUSANELLI, A ;
SUTTON, D .
ORGANOMETALLICS, 1994, 13 (03) :757-759