Synthesis, characterization and reactivity of cis-Ru (L)(PPh3) Cl2; L = 2-pyridyl-N-(2′-methylthiophenylmethyleneimine) crystal structure of cis-Ru(L)(PPh3)Cl2 and Ru(L)(PPh3)(bpy)2 (original) (raw)
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Organometallics, 1998
The tBu PONOP (2,6-bis(di-tert-butyl-phosphinito)pyridine) complexes of iron and cobalt, (tBu PONOP)FeCl 2 (1) and (tBu PONOP)CoCl 2 (2)) have been prepared. Both complexes are paramagnetic and the solid-state structures of 1 and 2 were determined by single crystal X-ray diffraction studies. Analogous Fe and Co complexes of the tBu PNP (2,6-bis(di-tert-butyl-phosphinomethyl)pyridine) ligand (3 and 4, respectively) were prepared to allow comparison between the closely related pincer ligands in the hydrosilylation of carbonyl moieties. All four complexes were found to be catalytically active when treated with NaBEt 3 H, which was assumed to generate a metal-hydride species in-situ.
Journal of Organometallic Chemistry, 2007
The Rh I , Ru II , Pd I and Ni II complexes of the aminobis(phosphonite), PhN(P(OC 6 H 4 OMe-o) 2) 2 (1) are reported. The reactions of 1 with [Rh(COD)Cl] 2 in 1:1 and 2:1 molar ratio afford the mono-and diolefin substituted chloro bridged chelate complexes, [(COD)Rh 2 (l 2-Cl) 2 {PhN(P(OC 6 H 4 OMe-o) 2) 2 }] (2) and [Rh(l 2-Cl){PhN(P(OC 6 H 4 OMe-o) 2) 2 }] 2 (3), respectively. Similarly, the cationic mono-and bis-chelate complexes, [Rh(COD){PhN(P(OC 6 H 4 OMe-o) 2) 2 }]OTf (4) and [Rh{PhN(P(OC 6 H 4 OMe-o) 2) 2 } 2 ]OTf (5) are obtained by treating 1 with [Rh(COD)Cl] 2 in the presence of AgOTf in appropriate ratios. The dinuclear Rh I carbonyl complex, [RhCl(CO){l-PhN(P(OC 6 H 4 OMe-o) 2) 2 }] 2 (6) is prepared by treating 1 with 0.5 equiv. of [Rh(CO) 2 Cl] 2. Reaction of 1 with cis-[NiBr 2 (DME)] (DME = 1,2-dimethoxyethane) affords [{PhN(P(OC 6 H 4 OMe-o) 2) 2 }NiBr 2 ] (7) whereas with [Ru-(g 6-p-cymene)Cl 2 ] 2 in refluxing THF medium produces an interesting and rare bimetallic Ru II complex, [(g 6-p-cymene)Ru(l 2-Cl) 3 Ru{PhN(P(OC 6 H 4 OMeo) 2) 2 }Cl] (8). Redox condensation of the Pd 0 and Pd II derivatives with 1 affords the dinuclear Pd I complex, [PdBr{l-PhN(P(O-C 6 H 4 OMe-o) 2) 2 }] 2 (9). The formation and structure of complexes 2-9 are assigned through various spectroscopic and micro analysis data. The molecular structures of 5 and 7-9 are confirmed by single crystal X-ray diffraction studies.
Synthesis, characterization, and reactivity of new ruthenium and osmium N2O2 complexes
Inorganic Chemistry, 1987
The tBu PONOP (2,6-bis(di-tert-butyl-phosphinito)pyridine) complexes of iron and cobalt, (tBu PONOP)FeCl 2 (1) and (tBu PONOP)CoCl 2 (2)) have been prepared. Both complexes are paramagnetic and the solid-state structures of 1 and 2 were determined by single crystal X-ray diffraction studies. Analogous Fe and Co complexes of the tBu PNP (2,6-bis(di-tert-butyl-phosphinomethyl)pyridine) ligand (3 and 4, respectively) were prepared to allow comparison between the closely related pincer ligands in the hydrosilylation of carbonyl moieties. All four complexes were found to be catalytically active when treated with NaBEt 3 H, which was assumed to generate a metal-hydride species in-situ.
Polyhedron, 2005
Ruthenium (II) complexes with the hemilabile ligand Ph 2 PCH 2 P(O)Ph 2 (dppmO) were obtained and characterized by 31 P{ 1 H} NMR, IR and cyclic voltammetry. The reaction of the compound tcc-[RuCl 2 (g 2 -dppmO) 2 ] with carbon monoxide yielded the complexes [RuCl 2 (CO)(g 1 ,g 2 -dppmO) 2 ] and [RuCl(CO)(g 2 -dppmO) 2 ]PF 6 . For the tcc-[RuCl 2 (g 2 -dppmO) 2 ] and [RuCl 2 (CO)(g 1 ,g 2 -dppmO) 2 ] species, two dimensional NMR analyses 31 P-31 P gCOSY, 13 C-1 H HSQC, 1 H-31 P HMBC were performed. Based on the resulting chemical shifts, coupling constants and correlations between 1 H, 13 C and 31 P spectra it was possible to reveal the structures of these complexes in solution. The structure of the tcc-[RuCl 2 (g 2 -dppmO) 2 ] complex was determined by X-ray diffraction, confirming the NMR results. The mer-[RuCl 3 (g 1 ,g 2 -dppmO) 2 ] complex was characterized by EPR and its crystal structure was also established by X-ray diffraction. The isomerization of tcc-[RuCl 2 (g 2 -dppmO) 2 ] into cct-[RuCl 2 (g 2 -dppmO) 2 ] was followed by UV-Vis spectroscopy and 31 P{ 1 H} NMR.
A series of Ru(III)-PyNHC complexes, identified as [RuIII(PyNHCR)(Cl)3(H2O)] (1ac), have been prepared following a base-free route. The structurally simple, air and moisture stable complexes represent rare examples of Ru(III)-NHC complexes. Further, these benchtop stable Ru(III)-PyNHC complexes were shown to be excellent metal precursors for the synthesis of new [RuII(PyNHCR)(Cl)2(PPh3)2] (2a-c) and [RuII(PyNHCR)(CNCMe)I]PF6 (3a-c) pincer complexes. All the complexes have been characterised using spectroscopic methods, and structures of 1a, 1b, 2c and 3a have been determined using the single-crystal X-ray diffraction technique.
Dalton Transactions, 2013
S1. General Experimental Methods S2. Synthesis of Ligands 1 and 2 2.1.1 Synthesis of 4'-(3,5-di(pyridin-4-yl)phenyl)-2,2':6',2''-terpyridine (1) 2.1.2 Synthesis of 4'-(3,5-bis(pyridin-4-ylethynyl)phenyl)-2,2':6',2''-terpyridine (2) S3. Synthesis and Characterisation of Fe(II) complexes 3.1.1 Synthesis of [Fe(1) 2 ](PF 6) 2 3.1.2 Synthesis of [Fe(2) 2 ](PF 6) 2 S4. Synthesis of Ru(II) complexes 4.1.1 Synthesis of Ru(4'-(3,5-dibromophenyl)-2,2':6':2''-terpyridine) 2 (PF 6) 2 Ru(5) 2 (PF 6) 2 4.1.2 Synthesis and Characterisation of [Ru(1) 2 ](PF 6) 2 4.1.3 Synthesis and Characterisation of [Ru(2) 2 ](PF 6) 2 S5. Synthesis of N-alkylated Ru(II) derivatives 5.1.1 Synthesis and Characterisation of [Ru(3a) 2 ](PF 6) 6 5.1.2 Synthesis and Characterisation of [Ru(4a) 2 ](PF 6) 6 5.1.3 Synthesis and Characterisation of [Ru(3b) 2 ](PF 6) 6 5.1.4 Synthesis and Characterisation of [Ru(4b) 2 ](PF 6) 6 S6. Summary of Absorption Data S7. Electrochemical Data 7.1.1 Cyclic Voltammograms of [Fe(1) 2 ](PF 6) 2 and [Ru(1) 2 ](PF 6) 2 7.1.2 Cyclic Voltammograms of [Fe(2) 2 ](PF 6) 2 and [Ru(2) 2 ](PF 6) 2 7.1.3 Cyclic Voltammograms of N-Me complexes [Ru(3a) 2 ](PF 6) 6 and [Ru(4a) 2 ](PF 6) 6 7.1.4 Cyclic Voltammograms of N-C 12 H 25 complexes [Ru(3b) 2 ](PF 6) 6 and [Ru(4b) 2 ](PF 6) 6 7.1.5 Electrochemical data for [Fe(4'-phenyl-(2,2':6',6''-terpyridine) 2 ](PF 6) 2 7.1.6 Differential Pulse Voltammetry (DPV) for [Ru(1) 2 ](PF 6) 2 , [Ru(3a) 2 ](PF 6) 6 and [Ru(3b) 2 ](PF 6) 6 7.1.7 Summary of electrochemical data S8. X-Ray diffraction experimental 8.1.1 General 8.1.2 Data for structure [Ru(1) 2 ]•2PF 6 •8.25H 2 O 8.1.3 Data for structure [Fe(1) 2 ]•2PF 6 •6MeNO 2 •12.5H 2 O 8.1.4 Data for structure 3 [Ru(1) 2 ]•5PF 6 •NO 3 8.1.5 Data for [Ru(2) 2 ](PF 6) 2 Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2013 S9. Host-Guest Interactions 9.1.1 Pillar[n]arenes 9.1.2 Metal-ion coordination by [Ru(3a) 2 ](PF 6) 2 9.1.3 Metal-ion coordination by [Ru(3b) 2 ](PF 6) 2 9.1.4 Association constant determinations S10. Additional References
Organometallics, 2013
The synthesis of novel PNN ruthenium pincer complexes based on 2,2′-dipyridinemethane phosphine derivatives, as well as on 2,2′-oxobispyridine phosphine ligands, and their reactivity toward dearomatization and cyclometalation are described. The dearomatized compounds 7a,b undergo cyclometalation to yield complexes 8a,b. In order for cyclometalation to proceed, the coordination sphere around the Ru center has to rearrange, and this depends on the flexibility of the system, showing that the cyclometalation is qualitatively faster in the case of the dimethyl derivative 7a than in the case of the spyrocyclopentyl derivative 7b. The cyclometalation occurs diastereoselectively and leads to only one diastereomer of the cyclometalated compounds. In the case of the 2,2′-oxobispyridine complex 6c, the dearomatized complex was too unstable to be isolated; however it was possible to isolate and characterize a stable dicarbonyl-dearomatized ruthenium(II) complex, 9c, when the deprotonation was performed under a CO atmosphere. Dearomatization of 6a under CO also led to dicarbonyl-dearomatized ruthenium(II) complex 9a, which slowly rearranged into the dicarbonyl-aromatized ruthenium(0) complex 10a. These complexes were tested in catalytic alcohol−amine coupling, esterification of primary alcohols, and hydrogenation of secondary amides. Moderate activity was observed in hydrogenation of amides to alcohols and amines and low activity in the other transformations, owing mainly to the formation of stable cyclometalated compounds. (M + 1) + ).
Polyhedron, 2010
This study presents the syntheses and characterization of 2-mercaptopyridine (pyS À ) complexes containing ruthenium(II) with the following general formula [Ru(pyS) 2 (P-P)], P-P = (c-dppen) = cis-1, and (dppb) = 1,4-bis(diphenylphosphino)butane (4). The complexes were synthesized from the mer-or fac-[RuCl 3 (NO)(P-P)] precursors in the presence of triethylamine in methanol solution with dependence of the product on the P-P ligand. The reaction of pyS À with a ruthenium complex containing a bulky aromatic diphosphine dppb disclosed a major product with a dangling coordinated dppbO-P, the [Ru(pyS) 2 (NO)(g 1 -dppbO-P)]PF 6 (5). In addition, this work also presents and discusses the spectroscopic and electrochemical behavior of 1-5, and report the X-ray structures for 1 and 5.
Journal of Organometallic Chemistry, 1993
The reaction of the ruthenium hydrides [Ru(CO)H(R'CN)z(PPh,)JA (A = CIO, or PF,) (R' = Me or CH,Ph) or the alkenyl derivatives [Ru(COXCH=CHR'XR'CN),XPPh,),~F, (R' = CMe,, Ph; R, = Me or CHzPh) with pyrazole or 3,5_dimethylpyrazole gives the ruthenium(H) pyrazolylamidine complexes [Ru(CO)H(NH=C(R'Xhet)~PPh3)2lA or [Ru(COXCH=CHCR*)(NH?c-(R*Xhet)XPPh,)JA, respectively (bet = pz or Mezpz). The stereochemistry of the resulting complexes has been determined by NOEDIFF experiments and by the X-ray structure determination of [Ru(COXCH4JHCMe,)@IH~MeXMezpz)~PPh3)z]PF6.