Synthesis, Characterization and Catalytic Properties of Benzylphosphonate-aminethylphosphine-Pd(II), Cu(II), Ru(II) and V(IV) Complexes (original) (raw)
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Ruthenium(II) complexes of benzylphosphines
Inorganic Chemistry, 1982
Reaction of the benzylphenylphosphines Bzl,,PPh, (L) with "Ru(CO),C12" produces the kinetically stable trans-L,Ru(CO),Cl, (l), which thermally isomerize to the thermodynamically stable C~S-L~RU(CO)~CI~ (2). The kinetics, activation thermodynamics, and mechanisms of these processes were determined by 31P NMR spectroscopy. The isomerization is a dissociative process (AS' and AH' are both positive) whose rate increases with an increase in the steric bulk of the phosphine and is retarded by excess carbon monoxide. A series of six complexes have been characterized by elemental analyses and infrared and IH, "C('H), and NMR spectroscopies. The crystal structures of trans-(B~l~P)~Ru(CO)~C1~ and cis-(B~lPPh~)~Ru(C0)~C1, have been determined from three-dimensional X-ray diffraction techniques. The structural data form a basis for discussion of the relative thermodynamic and kinetic stabilities of the isomers formed.
2007
The neutral Ru(II), chelating phosphine or diphosphine with 1,3-diamine (1,3-diamino-2-propanol) of type [RuCl2(PP)(NN)], are readily synthesized in very good yields at an inert atmosphere using dichloromethane as solvent. For the first time, the ruthenium(II) complexes: [trans-dichloro(bis(triphenylphosphine)(1,3-diamino-2-propanol)ruthenium(II)] (2), [trans-dichloro(1,3-bis(diphenylphosphino)propane)(1,3-diamino-2-propanol)ruthenium(II)] (4) and [trans-dichloro(bis(ether-phosphine)(1,3-diamino-2-propanol)ruthenium(II)] (6) have been prepared at room temperature starting from [RuCl2(PPh3)3], [RuCl2(Ph2PCH2CH2OCH3)2] and [RuCl2(dppp)2], respectively. Trans-RuCl2 with nitrogen atoms are trans to phosphorus atoms are structurally favored (kinetic) isomer. This structural phenomenon has been monitored by P{H} NMR in CD2Cl2. All the mentioned complexes were fully characterized by NMR, IR, and FAB-MS as well as elemental analysis.
Journal of Organometallic Chemistry, 2009
Ruthenium complexes [(g 5-C 5 H 5)Ru(j 1-P-PPh 2 Py)(PPh 3)Cl] (1) and [(g 5-C 5 H 5)Ru(j 2-P-N-PPh 2 Py)(PPh 3)] + (1a) containing diphenyl-2-pyridylphosphine (PPh 2 Py) are reported. Coordinated PPh 2 Py in the complex [(g 5-C 5 H 5)Ru(j 1-P-PPh 2 Py)(PPh 3)Cl] (1) exhibits monodentate behavior. In presence of NH 4 PF 6 in methanol at room temperature it afforded chelated complex [(g 5-C 5 H 5)Ru(j 2-P,N-PPh 2 Py)(PPh 3)] + (1a). Further, 1 reacted with various species viz., CH 3 CN, NaCN, NH 4 SCN and NaN 3 to afford cationic and neutral complexes [(g 5-C 5 H 5)Ru(j 1-P-PPh 2 Py)(PPh 3)L] + and [(g 5-C 5 H 5)Ru(j 1-P-PPh 2 Py)(PPh 3)L] [L = CH 3 CN (1b); CN À (1c); N 3 À (1d) and SCN À (1e)] and it's reaction with N,N-donor chelating ligands dimethylglyoxime (H 2 dmg) and 1,2-phenylenediamine (pda) gave cationic complexes [(g 5-C 5 H 5)Ru (j 1-P-PPh 2 Py)(j 2-N-N)]PF 6 [j 2-N-N = dmg (1f) and pda (1g)]. The complexes 1-1g have been characterized by physicochemical techniques and crystal structures of 1, 1a, 1c, 1e and 1f have been determined by single crystal X-ray analyses. Catalytic potential of the complex 1 has been evaluated in water under aerobic conditions. It was observed that the complex 1 selectively catalyzes reduction of aldehyde into alcohol.
Organometallics, 2005
The cis-[RuCl 2 (PPh 3 ) 2 (N-N)] (N-N ) bipy (1), Me-bipy (2), phen (3), and bathophen (4)) complexes were used to synthesize five new electron-rich phosphine-containing complexes cis-[RuCl 2 (dcype)(N-N)] (N-N ) bipy (1a), Me-bipy (2a), phen (3a), and bathophen (4a)) and cis-[RuCl 2 (PEt 3 ) 2 (bipy)] (1c) by phosphine exchange. These complexes were obtained and characterized by NMR ( 31 P{ 1 H}, 1 H), cyclic voltammetry, and elemental analysis. Electrochemical studies of these complexes reveal a single reduction process (Ru III /Ru II ). These complexes are more easily oxidized than their analogues cis-[RuCl 2 (dppb) ]. The reactivity of complexes cis-[RuCl 2 (dcype)(N-N)] with carbon monoxide was tested, and dissociation of one chloride was observed, leading to the formation of four new cationic species with general formula [RuCl(CO)(dcype)(N-N)](PF 6 ) (bipy (1b), Me-bipy (2b), phen (3b), and bathophen (4b)). The complexes described here and elsewhere with general formulas cis-[RuCl 2 (P-P)(N-N)], [RuCl(CO)(dcype)(N-N)](PF 6 ), and cis-[RuCl 2 (P) 2 (N-N)] were used as precatalysts in the transfer hydrogenation of functionalized aryl-ketones, and most of them were active. X-ray structures of cis-[RuCl 2 (PEt 3 ) 2 (bipy)] (1c) and [RuCl(CO)(dcype)(bipy)]-(PF 6 ) (1b) will be presented.
Polyhedron
Phosphine ruthenate complexes containing the non-innocent ligands 4-chloro-1,2-phenylenediamine (opda-Cl) and 3,3 0 ,4,4 0 -tetraamminebiphenyl (diopda) were synthesized and characterized by means of X-ray diffraction, electrochemistry, 31 P{ 1 H} NMR and electronic spectroscopies. Crystals of cis-[RuCl 2 (dppb)(bqdi-Cl)] complex were isolated as a mixture of two conformational isomers due to different positions of the chlorine atoms of the o-phenylene ligand in relation to the P1 atom of the phosphine moiety.
Ruthenium(II) complexes with triphenylphosphine or triphenylarsine and other monodentate ligands
Polyhedron, 1985
Synthesis and studies on some five-coordinate ruthenium(I1) complexes, viz. [Ru(MPh3)(CsH5CH0)2Cl,1 and [Ru(MPh&(CO)Cl,] (where M = P or As) have been described. Reactions of [Ru(MPh3)(CsH&HO),C1,] with N,N-dimethylformamide, dimethylsulphoxide and pyridine and of [Ru(MPh,), (CO)Cl,] with pyridine are described.
Polyhedron, 2013
We synthesized complexes with the general formula trans-[RuCl 2 (CO)(PR 3)(N-N)] (N-N = diimines and/ or amines; PR 3 = triphenylphosphine or trip -tolylphosphine) by reacting trans-[RuCl 2 (CO)(dmf)(PR 3) 2 ] (dmf = N,N-dimethylformamide) and the appropriate N-N donor ligands. We characterized the complexes by NMR (31 P, 1 H, nOe, HMBC, and HSQC), FTIR, and elemental analyses; we also analyzed trans-[RuCl 2 (CO)(PPh 3)(bipy)], trans, trans-[RuCl 2 (CO)(P{p-tol 3 })(ampy)] and trans, trans-[RuCl 2 (CO) (PPh 3)(ampy)] by X-ray diffraction. We tested the complexes as pre-catalyst for the reduction of acetophenone in transfer-hydrogenation conditions, using isopropanol as the hydrogen source. The catalyst/ base/substrate molar proportion of 1:20:1000 yielded conversions up to 83% in 24 h, whereas the proportion 1:20:500 furnished conversions up to 96% in 4 h. In addition, p-substituted acetophenone were reduced with conversions up to 95% within 135 min of reaction time. The complexes containing the ligands ampy and en were the most active-the ''RuH-NH'' unit promoted reactions via the outer-sphere mechanism.
Inorganic Chemistry, 2007
The half-sandwich complexes [(η 5-C 5 H 5)RuCl(DPEphos)] (1) and [{(η 6-p-cymene)RuCl 2 } 2 (µ-DPEphos)] (2) were synthesized by the reaction of bis(2-(diphenylphosphino)phenyl) ether (DPEphos) with a mixture of ruthenium trichloride trihydrate and cyclopentadiene and with [(η 6-p-cymene)RuCl 2 ] 2 , respectively. Treatment of DPEphos with cis-[RuCl 2-(dmso) 4 ] afforded fac-[RuCl 2 (κ 3-P,O,P-DPEphos)(dmso)] (3). The dmso ligand in 3 can be substituted by pyridine, 2,2′-bipyridine, 4,4′-bipyridine, and PPh 3 to yield trans,cis-[RuCl 2 (DPEphos)(C 5 H 5 N) 2 ] (4), cis,cis-[RuCl 2 (DPEphos)-(2,2′-bipyridine)] (5), trans,cis-[RuCl 2 (DPEphos)(µ-4,4′-bipyridine)] n (6), and mer,trans-[RuCl 2 (κ 3-P,P,O-DPEphos)-(PPh 3)] (7), respectively. Refluxing [(η 6-p-cymene)RuCl 2 ] 2 with DPEphos in moist acetonitrile leads to the elimination of the p-cymene group and the formation of the octahedral complex cis,cis-[RuCl 2 (DPEphos)(H 2 O)(CH 3 CN)] (8). The structures of the complexes 1−5, 7, and 8 are confirmed by X-ray crystallography. The catalytic activity of these complexes for the hydrogenation of styrene is studied.
Journal of Organometallic Chemistry, 2011
Reactions of the ruthenium complexes [Ru(k 3 -tpy)(PPh 3 )Cl 2 ], [Ru(k 3 -tptz)(PPh 3 )Cl 2 ] and [Ru(k 3 -tpy)Cl 3 ] [tpy ¼ 2,2 0 :6 0 ,2 00 -terpyridine; tptz ¼ 2,4,6-tris(2-pyridyl)-1,3,5-triazine] with diphenyl-(2-pyridyl)-phosphine (PPh 2 Py) have been investigated. The complexes [Ru(k 3 -tpy)(PPh 3 )Cl 2 ] and [Ru(k 3 -tptz)(PPh 3 )Cl 2 ] reacted with PPh 2 Py to afford [Ru(k 3 -tpy)(k 1 -P-PPh 2 Py) 2 Cl] þ (1) and [Ru(k 3 -tptz)(k 1 -P-PPh 2 Py) 2 Cl] þ (2), which were isolated as their tetrafluoroborate salts. Under analogous conditions, [Ru(k 3 -tpy)Cl 3 ] gave a neutral complex [Ru(k 3 -tpy)(k 1 -PPh 2 Py)Cl 2 ] (3). Upon treatment with an excess of NH 4 PF 6 in methanol, 1 and 2 gave [Ru(3 )](PF 6 ) 2 (9) supporting hemi labile nature of the coordinated PPh 2 Py. The complexes have been characterized by elemental analyses, spectral (IR, NMR, electronic absorption, FAB-MS), electrochemical studies and structures of 1, 2 and 3 determined by X-ray single crystal analyses. At higher concentration level (40 mM) the complexes under investigation exhibit inhibitory activity against DNA-Topo II of the filarial parasite S. cervi and 3 catalyses rearrangement of aldoximes to amide under aerobic conditions.