Base-assisted cyclometalation and phosphorus-carbon bond cleavage in (Arene)ruthenium(II) complexes containing functionalized iminophosphorane-phosphine ligands Ph2PCH2P{=NP(=X)(OR)2}Ph2 (X = O, S; R = Et, Ph)

被引:31
作者
Cadierno, V [1 ]
Díez, J [1 ]
Garcia-Alvarez, J [1 ]
Gimeno, J [1 ]
机构
[1] Univ Oviedo, Fac Quim, Inst Univ Quim Organomet Enrique Moles, Dept Quim Organ & Inorgan,CSIC,Unidad Asociada, E-33071 Oviedo, Spain
关键词
D O I
10.1021/om040033d
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Complexes [RuCl(eta(6)-p-cymene)(kappa(2)-P,X-Ph2PCH2P{=NP(=X)(OR)(2)}Ph-2)][SbF6] (X = O, R = Et (1a), Ph (1b); X = S, R = Et (2a), Ph (2b)) react with a stoichiometric amount of NaH, in THF at rt, to generate the neutral cyclometalated compounds [RuCl(kappa(2)-P,C-Ph2PCHP-{=NP(=X)(OR)(2)}Ph-2)( eta(6)-p-cymene)] (X = O, R = Et (3a), Ph (3b); X = S, R = Et (4a), Ph (4b)), via selective deprotonation of the methylenic backbone of the coordinated iminophosphorane-phosphine ligands. Treatment of 3-4a,b with AgSbF6, in CH2Cl2 at rt, affords the corresponding cationic species [Ru(kappa(3)-P,C,X-Ph2PCHP{=NP(=X)(OR)(2)}Ph-2)(eta(6)-p-cymene)]-[SbF6] (X = O, R = Et (7a), Ph (7b); X = S, R = Et (8a), Ph (8b)) through the intramolecular O- or S-coordination of the free -Ph2P=NP(=X)(OR)(2) fragment. Complexes 7-8a,b can also be prepared by reaction of the dicationic derivatives [Ru(eta(6)-p-cymene)(kappa(3)-P,N,X-Ph2PCH2P-{=NP(=X)(OR)(2)}Ph-2)] [SbF6](2) (5-6a,b) with 1 equiv of NaH. Formation of complexes 3-4a,b and 7-8a,b proceeds, in all cases, in a diastereoselective manner. Phosphorus-carbon bond splitting has been observed upon treatment of complexes 1-2a,b, 3-4a,b, or 7-8a,b with an excess of NaH, in wet THF at rt, affording the novel phosphinito derivatives [Ru(kappa(2)-C,X-CH2P{=NP(=X)(OR)(2)}Ph-2){kappa(1)-P-P(=O)Ph-2}(eta(6) -p-cymene)] (X = O, R = Et (10a); X = S, R = Et (11a), Ph (11b)). Protonation and methylation of 10-11 a,b generates the cationic species [Ru(kappa(2)-C,X-CH2P{=NP(=X)(OR)(2)}Ph-2){kappa(1)-P-P(OH)Ph-2}(eta(6)-p-eymene)] [BF4] (X = O, R = Et (12a); X = S, R = Et (13a), Ph (13b)) and [Ru(kappa(2)-C,X-CH2P{=NP(=X)(OR)(2)}Ph-2){kappa(1)-P-P(OMe)Ph-2}(eta(6)-p-cymene)] [CF3SO3] (X = O, R = Et (14a); X = S, R = Et (15a), Ph (15b)), respectively, via selective electrophilic addition at the Ph2P=O group. The structure of compounds [RuCl(kappa(2)-P,C-Ph2PCHP{=NP(=O)(OPh)(2)}Ph-2)(eta(6)-p-cymene)] (3b) and [Ru(kappa(2)-C,S-CH2P{=NP(=S)(OEt)(2)}Ph-2){kappa(1)-P-P(=O)Ph-2}(eta(6)-C6H6)] (11a') has been determined by X-ray crystallography.
引用
收藏
页码:3425 / 3436
页数:12
相关论文
共 89 条
[1]  
Alajarín M, 2000, SYNTHESIS-STUTTGART, P2085
[2]   TRANSITION METAL-CARBON BONDS .50. CONVERSION OF MER-[IRCL3-(PME2R)3] (R=ME OR PH) TO [IRCL2(CH2PMER)(PME2R)2] (3-MEMBERED RING) BY THE ACTION OF BASE - CRYSTAL-STRUCTURE OF [IRCL2(CH2PMEPH)(PME2PH)2] [J].
ALJIBORI, S ;
CROCKER, C ;
MCDONALD, WS ;
SHAW, BL .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1981, (07) :1572-1577
[3]   TABLES OF BOND LENGTHS DETERMINED BY X-RAY AND NEUTRON-DIFFRACTION .1. BOND LENGTHS IN ORGANIC-COMPOUNDS [J].
ALLEN, FH ;
KENNARD, O ;
WATSON, DG ;
BRAMMER, L ;
ORPEN, AG ;
TAYLOR, R .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1987, (12) :S1-S19
[4]  
[Anonymous], DIRDIF PROGRAM SYSTE
[5]  
[Anonymous], 1974, INT TABLES XRAY CRYS, VIV
[6]   P,N-heterodifunctional ligands by selective Staudinger reaction of β-substituted vinylazides with (Z)-1,2-bis(diphenylphosphanyl)-ethene and formation of cyclometalled complexes of palladium(II) of these ligands -: crystal and molecular structure of a new chiral cyclometallaphosphoraniminophosphane of palladium(II) [J].
Arques, A ;
Molina, P ;
Auñón, D ;
Vilaplana, MJ ;
Velasco, MD ;
Martínez, F ;
Bautista, D ;
Lahoz, FJ .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2000, 598 (02) :329-338
[7]   Versatile coordination behavior of (N-aryliminophosphoranyl)(thiophosphoranyl) methane and its anion to platinum(II) [J].
Avis, MW ;
Goosen, M ;
Elsevier, CJ ;
Veldman, N ;
Kooijman, H ;
Spek, AL .
INORGANICA CHIMICA ACTA, 1997, 264 (1-2) :43-60
[8]   REVERSIBLE METALATION OF ALKYL AND ARYL GROUPS BY A COORDINATIVELY UNSATURATED IRON COMPLEX [J].
BAKER, MV ;
FIELD, LD .
ORGANOMETALLICS, 1986, 5 (04) :821-823
[9]   HETEROFUNCTIONAL LIGANDS DERIVED FROM MONOOXIDIZED BIS(PHOSPHINO)AMINES - SYNTHESIS AND TRANSITION-METAL (RH(I), PD(II), PT(II)) COMPLEXES OF THE TRIPHOSPHORUS LIGANDS ((IMINOPHOSPHORANYL)AMINO)PHOSPHINE PHOSPHINIC OXIDES PH2PN(R)PH2P=NP(O)(OPH)2 (R = CH3, C2H5) - CRYSTAL AND MOLECULAR-STRUCTURES OF THE RHODIUM(I) AND PLATINUM(II) COMPLEXES (PHO)2(O)PN=PPH2N(C2H5)PH2PRH(CO)CL AND (PHO)2(O)PN=PPH2N(C2H5)PH2PPTCL2 [J].
BALAKRISHNA, MS ;
SANTARSIERO, BD ;
CAVELL, RG .
INORGANIC CHEMISTRY, 1994, 33 (14) :3079-3084
[10]   Synthesis and X-ray crystal structure of a novel long chain acyclic phosphazene, N,N′-{dimethyl-bis(diphenylphosphiniminophosphorane)} ethylenediamine {(PhO)2P(O)N=PN(CH3)CH2}2, obtained via a Staudinger reaction [J].
Balakrishna, MS ;
Abhyankar, RM ;
Walawalker, MG .
TETRAHEDRON LETTERS, 2001, 42 (14) :2733-2734