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1.
A series of ruthenium(II) acetonitrile, pyridine (py), carbonyl, SO2, and nitrosyl complexes [Ru(bdmpza)(O2CR)(L)(PPh3)] (L = NCMe, py, CO, SO2) and [Ru(bdmpza)(O2CR)(L)(PPh3)]BF4 (L = NO) containing the bis(3,5-dimethylpyrazol-1-yl)acetato (bdmpza) ligand, a N,N,O heteroscorpionate ligand, have been prepared. Starting from ruthenium chlorido, carboxylato, or 2-oxocarboxylato complexes, a variety of acetonitrile complexes [Ru(bdmpza)Cl(NCMe)(PPh3)] (4) and [Ru(bdmpza)(O2CR)(NCMe)(PPh3)] (R = Me (5a), R = Ph (5b)), as well as the pyridine complexes [Ru(bdmpza)Cl(PPh3)(py)] (6) and [Ru(bdmpza)(O2CR)(PPh3)(py)] (R = Me (7a), R = Ph (7b), R = (CO)Me (8a), R = (CO)Et (8b), R = (CO)Ph) (8c)), have been synthesized. Treatment of various carboxylato complexes [Ru(bdmpza)(O2CR)(PPh3)2] (R = Me (2a), Ph (2b)) with CO afforded carbonyl complexes [Ru(bdmpza)(O2CR)(CO)(PPh3)] (9a, 9b). In the same way, the corresponding sulfur dioxide complexes [Ru(bdmpza)(O2CMe)(PPh3)(SO2)] (10a) and [Ru(bdmpza)(O2CPh)(PPh3)(SO2)] (10b) were formed in a reaction of the carboxylato complexes with gaseous SO2. None of the 2-oxocarboxylato complexes [Ru(bdmpza)(O2C(CO)R)(PPh3)2] (R = Me (3a), Et (3b), Ph (3c)) showed any reactivity toward CO or SO2, whereas the nitrosyl complex cations [Ru(bdmpza)(O2CMe)(NO)(PPh3)](+) (11) and [Ru(bdmpza)(O2C(CO)Ph)(NO)(PPh3)](+) (12) were formed in a reaction of the acetato 2a or the benzoylformato complex 3c with an excess of nitric oxide. Similar cationic carboxylato nitrosyl complexes [Ru(bdmpza)(O2CR)(NO)(PPh3)]BF4 (R = Me (13a), R = Ph (13b)) and 2-oxocarboxylato nitrosyl complexes [Ru(bdmpza)(O2C(CO)R)(NO)(PPh3)]BF4 (R = Me (14a), R = Et (14b), R = Ph (14c)) are also accessible via a reaction with NO[BF4]. X-ray crystal structures of the chlorido acetonitrile complex [Ru(bdmpza)Cl(NCMe)(PPh3)] (4), the pyridine complexes [Ru(bdmpza)(O2CMe)(PPh3)(py)] (7a) and [Ru(bdmpza)(O2CC(O)Et)(PPh3)(py)] (8b), the carbonyl complex [Ru(bdmpza)(O2CPh)(CO)(PPh3)] (9b), the sulfur dioxide complex [Ru(bdmpza)(O2CPh)(PPh3)(SO2)] (10b), as well as the nitrosyl complex [Ru(bdmpza)(O2C(CO)Me)(NO)(PPh3)]BF4 (14a), are reported. The molecular structure of the sulfur dioxide complex [Ru(bdmpza)(O2CPh)(PPh3)(SO2)] (10b) revealed a rather unusual intramolecular SO2-O2CPh Lewis acid-base adduct. 相似文献
2.
Braun T Münch G Windmüller B Gevert O Laubender M Werner H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(11):2516-2530
The ethene derivatives [(eta(5)-C(5)R(5))RuX(C(2)H(4))(PPh(3))] with R=H and Me, which have been prepared from the eta(3)-allylic compounds [(eta(5)-C(5)R(5))Ru(eta(3)-2-MeC(3)H(4))(PPh(3))] (1, 2) and acids HX under an ethene atmosphere, are excellent starting materials for the synthesis of a series of new halfsandwich-type ruthenium(II) complexes. The olefinic ligand is replaced not only by CO and pyridine, but also by internal and terminal alkynes to give (for X=Cl) alkyne, vinylidene, and allene compounds of the general composition [(eta(5)-C(5)R(5))RuCl(L)(PPh(3))] with L=C(2)(CO(2)Me)(2), Me(3)SiC(2)CO(2)Et, C=CHCO(2)R, and C(3)H(4). The allenylidene complex [(eta(5)-C(5)H(5))RuCl(=C=C=CPh(2))(PPh(3))] is directly accessible from 1 (R=H) in two steps with the propargylic alcohol HC triple bond CC(OH)Ph(2) as the precursor. The reactions of the ethene derivatives [(eta(5)-C(5)H(5))RuX(C(2)H(4))(PPh(3))] (X=Cl, CF(3)CO(2)) with diazo compounds RR'CN(2) yield the corresponding carbene complexes [(eta(5)-C(5)R(5))RuX(=CRR')(PPh(3))], while with ethyl diazoacetate (for X=Cl) the diethyl maleate compound [(eta(5)-C(5)H(5))RuCl[eta(2)-Z-C(2)H(2)(CO(2)Et)(2)](PPh(3))] is obtained. Halfsandwich-type ruthenium(II) complexes [(eta(5)-C(5)R(5))RuCl(=CHR')(PPh(3))] with secondary carbenes as ligands, as well as cationic species [(eta(5)-C(5)H(5))Ru(=CPh(2))(L)(PPh(3))]X with L=CO and CNtBu and X=AlCl(4) and PF(6), have also been prepared. The neutral compounds [(eta(5)-C(5)H(5))RuCl(=CRR')(PPh(3))] react with phenyllithium, methyllithium, and the vinyl Grignard reagent CH(2)=CHMgBr by displacement of the chloride and subsequent C-C coupling to generate halfsandwich-type ruthenium(II) complexes with eta(3)-benzyl, eta(3)-allyl, and substituted olefins as ligands. Protolytic cleavage of the metal-allylic bond in [(eta(5)-C(5)H(5))Ru(eta(3)-CH(2)CHCR(2))(PPh(3))] with acetic acid affords the corresponding olefins R(2)C=CHCH(3). The by-product of this process is the acetato derivative [(eta(5)-C(5)H(5))Ru(kappa(2)-O(2)CCH(3))(PPh(3))], which can be reconverted to the carbene complexes [(eta(5)-C(5)H(5))RuCl(=CR(2))(PPh(3))] in a one-pot reaction with R(2)CN(2) and Et(3)NHCl. 相似文献
3.
Bruce MI Ellis BG Gaudio M Lapinte C Melino G Paul F Skelton BW Smith ME Toupet L White AH 《Dalton transactions (Cambridge, England : 2003)》2004,(10):1601-1609
Reactions between HC triple bond CC triple bond CSiMe3 and several ruthenium halide precursors have given the complexes Ru(C triple bond CC triple bond CSiMe3)(L2)Cp'[Cp'= Cp, L = CO (1), PPh3 (2); Cp' = Cp*, L2= dppe (3)]. Proto-desilylation of 2 and 3 have given unsubstituted buta-1,3-diyn-1-yl complexes Ru(C triple bond CC triple bond CH)(L2)Cp'[Cp'= Cp, L = PPh3 (5); Cp'= Cp*, L2 = dppe (6)]. Replacement of H in 5 or 6 with Au(PR3) groups was achieved in reactions with AuCl(PR3) in the presence of KN(SiMe3)2 to give Ru(C triple bond CC triple bond CAu(PR3)](L2)Cp'[Cp' = Cp, L = PPh3, R = Ph (7); Cp' = Cp*, L2= dppe, R = Ph (8), tol (9)]. The asymmetrically end-capped [Cp(Ph3P)2Ru]C triple bond CC triple bond C[Ru(dppe)Cp*] (10) was obtained from Ru(C triple bond CC triple bond CH)(dppe)Cp* and RuCl(PPh3)2Cp. Single-crystal X-ray structural determinations of and are reported, with a comparative determination of the structure of Fe(C triple bond CC triple bond CSiMe3)(dppe)Cp* (4), and those of a fifth polymorph of [Ru(PPh3)2Cp]2(mu-C triple bond CC triple bond C) (12), and [Ru(dppe)Cp]2(mu-C triple bond CC triple bond C) (13). 相似文献
4.
Secondary phosphine complexes of the formula [(eta(5)-C(5)H(5))Ru(L)(2)(PHR(2))](+) BAr(F)(-) are prepared from cationic ruthenium N(2) complexes and PHR(2) (R = Ph (a), t-Bu (b), Cy (c)). Additions of t-BuOK or NaN(SiMe(3))(2) give the phosphido complexes (eta(5)-C(5)H(5))Ru(L)(2)(PR(2)) ((L)(2) = (PEt(3))(2) (5a-c), depe (6a,b)) in high NMR yields. These rapidly oxidize in air to give isolable RuP(=O)R(2) species. Complex 5a is more basic than the rhenium analogue (eta(5)-C(5)H(5))Re(NO)(PPh(3))(PPh(2)), and 6b is more basic than P-t-Bu(3). Complexes 5a-c and 6b are effective ligands for palladium-catalyzed Suzuki reactions. The catalyst from 6b is nearly as reactive as that from the benchmark ligand P-t-Bu(3). 相似文献
5.
31P CP/MAS NMR spectroscopy is examined as a method of characterization for ruthenium(II) phosphine complexes in the solid state, and the results are compared with X-ray crystallographic data determined for RuCl(2)(dppb)(PPh(3)) (dppb = Ph(2)P(CH(2))(4)PPh(2)), RuBr(2)(PPh(3))(3), and the previously determined RuCl(2)(PPh(3))(3). Crystals of RuBr(2)(PPh(3))(3) (C(54)H(45)Br(2)P(3)Ru) are monoclinic, space group P2(1)/a, with a = 12.482(4) ?, b = 20.206(6) ?, c = 17.956(3) ?, beta = 90.40(2) degrees, and Z = 4, and those of RuCl(2)(dppb)(PPh(3)) (C(46)H(43)Cl(2)P(3)Ru) are also monoclinic, space group P2(1)/n, with a = 10.885(2) ?, b = 20.477(1) ?, c = 18.292(2) ?, beta = 99.979(9) degrees, and Z = 4. The structure of RuBr(2)(PPh(3))(3) was solved by direct methods, and that of RuCl(2)(dppb)(PPh(3)) was solved by the Patterson method. The structures were refined by full-matrix least-squares procedures to R = 0.048 and 0.031 (R(w) = 0.046 and 0.032) for 5069 and 5925 reflections with I >/= 3sigma(I), respectively. Synthetic routes to RuBr(2)(dppb)(PPh(3)) and [RuBr(dppb)](2)(&mgr;(2)-dppb) are reported. The reactivity of RuCl(2)(dppb)(PPh(3)) with the neutral two-electron donor ligands (L) dimethyl sulfoxide, tetramethylene sulfoxide, tetrahydrothiophene, and dimethyl sulfide to give [(L)(dppb)Ru(&mgr;-Cl)(3)RuCl(dppb)] is discussed. 相似文献
6.
Lai CY Mak WL Chan EY Sau YK Zhang QF Lo SM Williams ID Leung WH 《Inorganic chemistry》2003,42(19):5863-5870
Treatment of 2-(methylsulfinyl)benzaldehyde (1) with ethylenediamine or (1R,2R)-(-)-1,2-diaminocyclohexane afforded N,N'-bis[2-(methylsulfinyl)benzylidene]ethylenediamine (L(1)) or (1R,2R)-N,N'-bis[2-(methylsulfinyl)benzylidene]-1,2-cyclohexanedia mine (L(2)), respectively. Lithiation of 2-bromobenzaldehyde diethylacetal with n-BuLi/TMEDA followed by reaction with (1R,2S,5R)-(-)-menthyl-(S)-p-toluenesulfinate afforded 2-(S)-(p-tolylsulfinyl)benzaldehyde diethyl acetal (2). Deprotection of 2 with pyridinium tosylate followed by condensation with ethylenediamine, (1R,2R)-(-)-diaminocyclohexane, or (S,S)-(+)-diaminocyclohexane afforded N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]ethylenediamine (L(3)), (1R,2R)-N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanediamine ((R,R)-L(4)), or (S,S)-N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanediamine ((S,S)-L(4)), respectively. Treatment of [Ru(PPh(3))(3)Cl(2)] with L afforded trans-[Ru(L)Cl(2)] [L = L(1) (3), L(2) (4), L(3) (5), (R,R)-L(4) ((R,R)-6), (S,S)-L(4) ((S,S)-6)]. The X-ray structures of (S(S),R(S))-4, (R,R)-6, and (S,S)-6 have been determined. The average Ru-N, Ru-S, and Ru-Cl distances in (S(S),R(S))-4 are 2.063, 2.2301, and 2.4039 A, respectively. The corresponding distances in (R,R)-6 are 2.071, 2.256, and 2.411 A, and those in (S,S)-6, 2.058, 2.2275, and 2.3831 A. Compound 3 exhibited a reversible Ru(III/II) couple at 0.56 V vs Cp(2)Fe(+/0) in CH(2)Cl(2). Treatment of 3 with AgNO(3) in water afforded the aqua compound trans-[Ru(L(1))Cl(H(2)O)][PF(6)] (7), which has been characterized by X-ray crystallography. The Ru-Cl, Ru-O, average Ru-N, and average Ru-S distances in 7 are 2.3733(6), 2.1469(16), 2.071, and 2.2442 A, respectively. Treatment of 3 with AgNO(3) followed by reaction with PPh(3) afforded [Ru(L(1))(PPh(3))(2)][PF(6)](2) (8). Treatment of [Os(PPh(3))(3)Cl(2)] with L(1) resulted in deoxygenation of one sulfoxide group of L(1) and formation of [Os(L(5))Cl(2)(PPh(3))] (9) (L(5) = N-[2-(methylsulfinyl)benzylidene]-N'-[2-(methylthio)benzylididene]ethylenediamine), which has been characterized by X-ray crystallography. The average Os-S(O), Os-N(trans to P), Os-N(trans to S), Os-P, and Os-Cl distances are 2.1931, 2.085, 2.175, 2.3641, and 2.4266 A, respectively. 相似文献
7.
Joslin EE McMullin CL Gunnoe TB Cundari TR Sabat M Myers WH 《Inorganic chemistry》2012,51(8):4791-4801
The complexes TpRu[P(OCH(2))(2)(OCCH(3)](PPh(3))Cl (2) [Tp = hydridotris(pyrazolyl)borate; P(OCH(2))(2)(OCCH(3)) (1) = (4-methyl-2,6,7-trioxa-1-phosphabicyclo[2,2,1]heptane] and TpRu(L)(PPh(3))Cl [L = P(OCH(2))(3)CEt (3), PMe(3) (4) or P(OMe)(3) (5)], (η(6)-C(6)H(6))Ru(L)Cl(2) [L = PPh(3) (6), P(OMe)(3) (7), PMe(3) (8), P(OCH(2))(3)CEt (9), CO (10) or P(OCH(2))(2)(OCCH(3)) (11)] and (η(6)-p-cymene)Ru(L)Cl(2) [L = P(OCH(2))(3)CEt (12), P(OCH(2))(2)(OCCH(3))P(OCH(2))(2)(OCCH(3)) (13), P(OMe)(3) (14) or PPh(3) (15)] have been synthesized, isolated, and characterized by NMR spectroscopy, cyclic voltammetry, mass spectrometry, and, for some complexes, single crystal X-ray diffraction. Data from cyclic voltammetry and solid-state structures have been used to compare the properties of (1) with other phosphorus-based ligands as well as carbon monoxide. Data from the solid-state structures of Ru(II) complexes show that P(OCH(2))(2)(OCCH(3)) has a cone angle of 104°. Cyclic voltammetry data reveal that the Ru(II) complexes bearing P(OCH(2))(2)(OCCH(3)) have more positive Ru(III/II) redox potentials than analogous complexes with the other phosphorus ligands; however, the Ru(III/II) potential for (η(6)-C(6)H(6))Ru[P(OCH(2))(2)(OCCH(3))]Cl(2) is more negative compared to the Ru(III/II) potential for the CO complex (η(6)-C(6)H(6))Ru(CO)Cl(2). For the Ru(II) complexes studied herein, these data are consistent with the overall donor ability of 1 being less than other common phosphines (e.g., PMe(3) or PPh(3)) or phosphites [e.g., P(OCH(2))(3)CEt or P(OMe)(3)] but greater than carbon monoxide. 相似文献
8.
The treatment of [Ru(L(OEt))(N)Cl(2)] (1; L(OEt)(-) = [Co(η(5)-C(5)H(5)){P(O)(OEt)(2)}(3)](-)) with Et(3)SiH affords [Ru(L(OEt))Cl(2)(NH(3))] (2), whereas that with [Ru(L(OEt))(H)(CO)(PPh(3))] (3) gives the dinuclear imido complex [(L(OEt))Cl(2)Ru(μ-NH)Ru(CO)(PPh(3))(L(OEt))] (4). The imido group in 4 binds to the two ruthenium atoms unsymmetrically with Ru-N distances of 1.818(6) and 1.952(6) ?. The reaction between 1 and 3 at 25 °C in a toluene solution is first order in both complexes with a second-order rate constant determined to be (7.2 ± 0.4) × 10(-5) M(-1) s(-1). 相似文献
9.
Baratta W Ballico M Baldino S Chelucci G Herdtweck E Siega K Magnolia S Rigo P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(30):9148-9160
New benzo[h]quinoline ligands (HCN'N) containing a CHRNH2 (R=H (a), Me (b), tBu (c)) function in the 2-position were prepared starting from benzo[h]quinoline N-oxide (in the case of ligand a) and 2-chlorobenzo[h]quinoline (for ligands b and c). These compounds were used to prepare ruthenium and osmium complexes, which are excellent catalysts for the transfer hydrogenation (TH) of ketones. The reaction of a with [RuCl2(PPh3)3] in 2-propanol at reflux afforded the terdentate CN'N complex [RuCl(CN'N)(PPh3)2] (1), whereas the complexes [RuCl(CN'N)(dppb)] (2-4; dppb=Ph2P(CH2)4PPh2) were obtained from [RuCl2(PPh3)(dppb)] with a-c, respectively. Employment of (R,S)-Josiphos, (S,R)-Josiphos*, (S,S)-Skewphos, and (S)-MeO-Biphep in combination with [RuCl2(PPh3)3] and ligand a gave the chiral derivatives [RuCl(CN'N)(PP)] (5-8). The osmium complex [OsCl(CN'N)(dppb)] (12) was prepared by treatment of [OsCl2(PPh3)3] with dppb and ligand a. Reaction of the chloride 2 and 12 with NaOiPr in 2-propanol/toluene afforded the hydride complexes [MH(CN'N)(dppb)] (M=Ru 10, Os 14), through elimination of acetone from [M(OiPr)(CN'N)(dppb)] (M=Ru 9, Os 13). The species 9 and 13 easily reacted with 4,4'-difluorobenzophenone, via 10 and 14, respectively, affording the corresponding isolable alkoxides [M(OR)(CN'N)(dppb)] (M=Ru 11, Os 15). The complexes [MX(CN'N)(P2)] (1-15) (M=Ru, Os; X=Cl, H, OR; P=PPh3 and P2=diphosphane) are efficient catalysts for the TH of carbonyl compounds with 2-propanol in the presence of NaOiPr (2 mol %). Turnover frequency (TOF) values up to 1.8x10(6) h(-1) have been achieved using 0.02-0.001 mol % of catalyst. Much the same activity has been observed for the Ru--Cl, --H, --OR, and the Os--Cl derivatives, whereas the Os--H and Os--OR derivatives display significantly lower activity on account of their high oxygen sensitivity. The chiral Ru complexes 5-8 catalyze the asymmetric TH of methyl-aryl ketones with TOF approximately 10(5) h(-1) at 60 degrees C, up to 97 % enatiomeric excess (ee) and remarkably high productivity (0.005 mol % catalyst loading). High catalytic activity (TOF up to 2.2x10(5) h(-1)) and enantioselectivity (up to 98 % ee) have also been achieved with the in-situ-generated catalysts prepared from [MCl2(PPh3)3], (S,R)-Josiphos or (S,R)-Josiphos*, and the benzo[h]quinoline ligands a-c. 相似文献
10.
Reactions of coordinatively unsaturated Ru[N(Ph2PQ)2]2(PPh3) (Q = S (1), Se (2)) with pyridine (py), SO2, and NH3 afford the corresponding 18e adducts Ru[N(Ph2PQ)2]2(PPh3)(L) (Q = S, L = NH3 (5); Q = Se, L = py (3), SO2 (4), NH3 (6)). The molecular structures of complexes 2 and 6 are determined. The geometry around Ru in 2 is pseudo square pyramidal with PPh3 occupying the apical position, while that in 6 is pseudooctahedral with PPh3 and NH3 mutually cis. The Ru-P distances in 2 and 6 are 2.2025(11) and 2.2778(11) A, respectively. The Ru-N bond length in 6 is 2.185(3) A. Treatment of 1 or 2 with substituted hydrazines L or NH2OH yields the respective adducts Ru[N(Ph2PQ)2]2(PPh3)(L) (Q = S, L = NH2NH2 (12), t-BuNHNH2 (14), l-aminopiperidine (C5H10NNH2) (15); Q = Se, L = PhCONHNH2 (7), PhNHNH2 (8), NH2OH (9), t-BuNHNH2 (10), C5H10NNH2 (11), NH2NH2 (13)), which are isolated as mixtures of their trans and cis isomers. The structures of cis-14 and cis-15 are characterized by X-ray crystallography. In both molecular structures, the ruthenium adopts a pseudooctahedral arrangement with PPh3 and hydrazine mutually cis. The Ru-N bond lengths in cis-14.CH2Cl2 and cis-15 are 2.152(3) and 2.101(3) A, respectively. The Ru-N-N bond angles in cis-14.CH2Cl2 and cis-15 are 120.5(4) and 129.0(2) degrees, respectively. Treatment of 1 with hydrazine monohydrate leads to the isolation of yellow 5 and red trans-Ru[N(Ph2PS)2]2(NH3)(H2O) (16), which are characterized by mass spectrometry, 1H NMR spectroscopy, and elemental analyses. The geometry around ruthenium in 16 is pseudooctahedral with the NH3 and H2O ligands mutually trans. The Ru-O and Ru-N bond distances are 2.118(4) and 2.142(6) A, respectively. Oxidation reactions of the above ruthenium hydrazine complexes are also studied. 相似文献
11.
Conner D Jayaprakash KN Wells MB Manzer S Gunnoe TB Boyle PD 《Inorganic chemistry》2003,42(15):4759-4772
The octahedral Ru(II) amine complexes [TpRu(L)(L')(NH(2)R)][OTf] (L = L' = PMe(3), P(OMe)(3) or L = CO and L' = PPh(3); R = H or (t)Bu) have been synthesized and characterized. Deprotonation of the amine complexes [TpRu(L)(L')(NH(3))][OTf] or [TpRu(PMe(3))(2)(NH(2)(t)Bu)][OTf] yields the Ru(II) amido complexes TpRu(L)(L')(NH(2)) and TpRu(PMe(3))(2)(NH(t)Bu). Reactions of the parent amido complexes or TpRu(PMe(3))(2)(NH(t)Bu) with phenylacetylene at room temperature result in immediate deprotonation to form ruthenium-amine/phenylacetylide ion pairs, and heating a benzene solution of the [TpRu(PMe(3))(2)(NH(2)(t)Bu)][PhC(2)] ion pair results in the formation of the Ru(II) phenylacetylide complex TpRu(PMe(3))(2)(C[triple bond]CPh) in >90% yield. The observation that [TpRu(PMe(3))(2)(NH(2)(t)Bu)][PhC(2)] converts to the Ru(II) acetylide with good yield while heating the ion pairs [TpRu(L)(L')(NH(3))][PhC(2)] yields multiple products is attributed to reluctant dissociation of ammonia compared with the (t)butylamine ligand (i.e., different rates for acetylide/amine exchange). These results are consistent with ligand exchange reactions of Ru(II) amine complexes [TpRu(PMe(3))(2)(NH(2)R)][OTf] (R = H or (t)Bu) with acetonitrile. The previously reported phenyl amido complexes TpRuL(2)(NHPh) [L = PMe(3) or P(OMe)(3)] react with 10 equiv of phenylacetylene at elevated temperature to produce Ru(II) acetylide complexes TpRuL(2)(C[triple bond]CPh) in quantitative yields. Kinetic studies indicate that the reaction of TpRu(PMe(3))(2)(NHPh) with phenylacetylene occurs via a pathway that involves TpRu(PMe(3))(2)(OTf) or [TpRu(PMe(3))(2)(NH(2)Ph)][OTf] as catalyst. Reactions of 1,4-cyclohexadiene with the Ru(II) amido complexes TpRu(L)(L')(NH(2)) (L = L' = PMe(3) or L = CO and L' = PPh(3)) or TpRu(PMe(3))(2)(NH(t)Bu) at elevated temperatures result in the formation of benzene and Ru hydride complexes. TpRu(PMe(3))(2)(H), [Tp(PMe(3))(2)Ru[double bond]C[double bond]C(H)Ph][OTf], [Tp(PMe(3))(2)Ru=C(CH(2)Ph)[N(H)Ph]][OTf], and [TpRu(PMe(3))(3)][OTf] have been independently prepared and characterized. Results from solid-state X-ray diffraction studies of the complexes [TpRu(CO)(PPh(3))(NH(3))][OTf], [TpRu(PMe(3))(2)(NH(3))][OTf], and TpRu(CO)(PPh(3))(C[triple bond]CPh) are reported. 相似文献
12.
Ciganda R Garralda MA Ibarlucea L Mendicute-Fierro C Torralba MC Torres MR 《Inorganic chemistry》2012,51(3):1760-1768
The hydridoirida-β-diketone [IrHCl{(PPh(2)(o-C(6)H(4)CO))(2)H}] (1) reacts with benzylamine (C(6)H(5)CH(2)NH(2)) to give the hydridoirida-β-ketoimine [IrHCl{(PPh(2)(o-C(6)H(4)CO))(PPh(2)(o-C(6)H(4)CNCH(2)C(6)H(5)))H}] (2), stabilized by an intramolecular hydrogen bond. 2 reacts with water to undergo hydrolysis and amine coordination giving hydridodiacylamino [IrH(PPh(2)(o-C(6)H(4)CO))(2)(C(6)H(5)CH(2)NH(2))] (3). Cyclohexylamine or dimethylamine lead to hydridodiacylamino [IrH(PPh(2)(o-C(6)H(4)CO))(2)L] (4-5). In chlorinated solvents hydridodiacylamino complexes undergo exchange of hydride by chloride to afford [IrCl(PPh(2)(o-C(6)H(4)CO))(2)L] (6-9). The reaction of 1 with hydrazine (H(2)NNH(2)) gives hydridoirida-β-ketoimine [IrHCl{(PPh(2)(o-C(6)H(4)CO))(PPh(2)(o-C(6)H(4)CNNH(2)))H}] (10), fluxional in solution with values for ΔH(?) of 2.5 ± 0.3 kcal mol(-1) and for ΔS(?) of -32.9 ± 3 eu. A hydrolysis/imination sequence can be responsible for fluxionality. 2-Aminopyridines (RHNC(5)H(3)R'N) react with 1 to afford cis-[IrCl(PPh(2)(o-C(6)H(4)CO))(PPh(2)(o-C(6)H(4)CHNRC(5)H(3)R'N))] (R = R' = H (11), R = CH(3), R' = H (12), R = H, R' = CH(3) (13)) containing new terdentate PCN ligands in a facial disposition and cis phosphorus atoms as kinetic products. The formation of 11-13 requires imination of the hydroxycarbene moiety of 1, coordination of the nitrogen atom of pyridine to iridium, and iridium to carbon hydrogen transfer. In refluxing methanol, complexes 11-13 isomerize to afford the thermodynamic products 14-16 with trans phosphorus atoms. Chloride abstraction from complexes [IrCl(PPh(2)(o-C(6)H(4)CO))(PPh(2)(o-C(6)H(4)CHNRC(5)H(4)N))] (R = H or CH(3)) leads to decarbonylation of the acylphosphine chelating group to afford cationic complexes [Ir(CO)(PPh(2)(o-C(6)H(4)))(PPh(2)(o-C(6)H(4)CHNRC(5)H(4)N))]A, 17 (R = H, A = ClO(4)) and 18 (R = CH(3), A = BF(4)) as a cis/trans = 4:1 mixture of isomers. Single crystal X-ray diffraction analysis was performed on 6, 9, 13, and 14. 相似文献
13.
Ara I Forniés J García A Gómez J Lalinde E Moreno MT 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(16):3698-3716
The reactions between cis-[M(C(6)F(5))(2)(PPh(2)CtriplebondCR)(2)] (M=Pt, Pd; R=Ph, tBu, Tol 2, 3) or cis-[Pt(C(6)F(5))(2)(PPh(2)CtriplebondCR)(PPh(2)CtriplebondCtBu)] (R=Ph 4, Tol 5) and cis-[Pt(C(6)F(5))(2)(thf)(2)] 1 have been investigated. Whereas [M](PPh(2)CtriplebondCtBu)(2) ([M]=cis-M(C(6)F(5))(2)) is inert towards 1, the analogous reactions starting from [M](PPh(2)CtriplebondCR)(2) or [Pt](PPh(2)CtriplebondCR)(PPh(2)CtriplebondCtBu) (R=Ph, Tol) afford unusual binuclear species [Pt(C(6)F(5))(S)mu-[C(R')dbondC(PPh(2))C(PPh(2))doublebondC(R)(C(6)F(5))]M(C(6)F(5))(2)] (R=R'=Ph, Tol, M=Pt 6 a,c, M=Pd 7 a,c; M=Pt, R'=tBu, R=Ph 8, Tol 9) containing a bis(diphenylphosphanyl)butadienyl bridging ligand formed by an unprecedented sequential insertion reaction of two P-coordinated PPh(2)CtriplebondCR ligands into a PtbondC(6)F(5) bond. Although in solution the presence of coordinated solvent S (S=(thf)(x)(H(2)O)(y)) in 6, 7 is suggested by NMR spectroscopy, X-ray diffraction analyses of different crystals of the mixed complex [Pt(C(6)F(5))mu-[C(tBu)doublebondC(PPh(2))C(PPh(2))doublebondC(Tol)(C(6)F(5))]Pt(C(6)F(5))(2)] 9 unequivocally establish that in the solid state the steric crowding of the new diphenylbutadienyl ligand formed stabilizes an unusual coordinatively unsaturated T-shaped 3-coordinated platinum(II) center. Structure determinations of the mononuclear precursors cis-[Pt(C(6)F(5))(2)(PPh(2)CtriplebondCR)(2)] (R=Ph, tBu, Tol) have been carried out to evaluate the factors affecting the insertion processes. The reactions of the platinum complexes 6 towards neutral ligands (L=CO, py, PPh(2)H, CNtBu) in a 1:1 molar ratio afford related diplatinum derivatives 10-13, whereas treatment with CNtBu (1:2 molar ratio) or 2,2'-bipy (1:1 molar ratio) results in the opening of the chelating ring to give cis,cis-[Pt(C(6)F(5))(L)(2)mu-[1-kappaC(1):2-kappaPP'-C(R)doublebondC(PPh(2))C(PPh(2))doublebondC(R)(C(6)F(5))]Pt(C(6)F(5))(2)] (14, 15). The unsaturated or solvento complexes are unstable in solution evolving firstly, through an unexpected formal 4-1 R (Ph, Tol) migration, to the intermediate diphosphanylbutadienyl isomer derivatives [Pt(C(6)F(5))(S)mu-[C(C(6)F(5))doublebondC(PPh(2))C(PPh(2))doublebondC(R)(2)]M(C(6)F(5))(2)] (16, 18) (X-ray, R=Ph, M=Pt) and, finally, to 1-pentafluorophenyl-2,3-bis(diphenylphosphanyl)naphthalene mononuclear complexes (17, 19) by annulation of a phenyl or tolyl group. 相似文献
14.
Reaction of benzaldehyde semicarbazone (HL-R, where H is a dissociable proton and R is a substituent (R = OMe, Me, H, Cl, NO(2)) at the para position of the phenyl ring) with [Ru(PPh(3))(3)Cl(2)] and [Ru(PPh(3))(2)(CO2)Cl2] has afforded complexes of different types. When HL-NO(2) and [Ru(PPh(3))(3)Cl2] react in solution at ambient temperature, trans-[Ru(PPh(3))(2)(L-NO2Cl] is obtained. Its structure determination by X-ray crystallography shows that L-NO2 is coordinated as a tridentate C,N,O-donor ligand. When reaction between HL-NO2 and [Ru(PPh(3))(3)Cl2] is carried out in refluxing ethanol, a more stable cis isomer of [Ru(PPh(3))(2)(L-NO2)Cl] is obtained. The trans isomer can be converted to the cis isomer simply by providing appropriate thermal energy. Slow reaction of HL-R with [Ru(PPh(3))(2)(CO2)Cl2] in solution at ambient temperature yields 5-[Ru(PPh(3))(2)(L-R)(CO)Cl] complexes. A structure determination of 5-[Ru(PPh(3))(2)(L-NO2)(CO)Cl] shows that the semicarbazone ligand is coordinated as a bidentate N,O-donor, forming a five-membered chelate ring. When reaction between HL-R and [Ru(PPh(3))(2)(CO2Cl2] is carried out in refluxing ethanol, the 4-[Ru(PPh(3))(2)(L-R)(CO)Cl] complexes are obtained. A structure determination of 4-[Ru(PPh(3))(2)(L-NO2)(CO)Cl] shows that a semicarbazone ligand is bound to ruthenium as a bidentate N,O-donor, forming a four-membered chelate ring. All the complexes are diamagnetic (low-spin d(6), S = 0). The trans- and cis-[Ru(PPh(3))(2)(L-NO2)Cl] complexes undergo chemical transformation in solution. The 5- and 4-[Ru(PPh(3))(2)(L-R)(CO)Cl] complexes show sharp NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry of the 5-[Ru(PPh(3))(2)(L-R)(CO)Cl] and 4-[Ru(PPh(3))(2)(L-R)(CO)Cl] complexes show the Ru(II)-Ru(III) oxidation to be within 0.66-1.07 V. This oxidation potential is found to linearly correlate with the Hammett constant of the substituent R. 相似文献
15.
Liu D Dang L Sun Y Chan HS Lin Z Xie Z 《Journal of the American Chemical Society》2008,130(47):16103-16110
A hydrogen-mediated Ru-C to Ru-B bond conversion was observed experimentally and supported by the theoretical calculations. Treatment of [eta(5):sigma(C)-Me(2)C(C(5)H(4))(C(2)B(10)H(10))]Ru(COD) (1) bearing a Ru-C(cage) sigma bond with PR(3) in the presence of H(2) gave Ru-B(cage) bonded complexes [eta(5):sigma(B)-Me(2)C(C(5)H(4))(C(2)B(10)H(10))]RuH(2)(PR(3)) (R = Cy (2), Ph (3)) (sigma(C): Ru-C(cage) sigma bond; sigma(B): Ru-B(cage) sigma bond). Complex 3 was converted to [eta(5):sigma(B)-Me(2)C(C(5)H(4))(C(2)B(10)H(10))]Ru(L(2)) in the presence of L(2) (L(2) = dppe (4), PPh(3)/P(OEt)(3) (5), PPh(3)/pyridine (6)) via liberation of H(2) upon heating. These complexes were fully characterized by various spectroscopic techniques, elemental analyses, and single-crystal X-ray diffraction studies. DFT calculations show that this conversion process is both kinetically and thermodynamically favorable and requires involvement of a hydride ligand. 相似文献
16.
The reaction of Ru(Me(2)bipy)(PPh(3))(2)Cl(2) 1 with terminal alkynes HCCR in the presence of TlPF(6) leads to the formation of the vinylidene compounds [Ru(Me(2)bipy)(PPh(3))(2)Cl(=C=CHR)][PF(6)] (2) (2a, R = Bu(t); 2b, R = p-C(6)H(4)-Me; 2c, R = Ph). These compounds decompose in oxygenated solution to form the carbonyl compound [Ru(Me(2)bipy)(PPh(3))(2)Cl(CO)][PF(6)] (3), and may be deprotonated by K(2)CO(3) to give the ruthenium(II) terminal acetylide compounds Ru(Me(2)bipy)(PPh(3))(2)Cl(CC-R) (4) (4a, R = Bu(t); 4b, R = p-C(6)H(4)-Me; 4c, R = Ph). Cyclic voltammetry shows that 2a-c may also be reductively dehydrogenated to form 4a-c. 4a-c are readily oxidized to their ruthenium(III) analogues [4a](+)-[4c](+), and the changes seen in their UV/visible spectra upon performing this oxidation are analyzed. These show that whereas the UV/visible spectra of 4a-c show MLCT bands from the ruthenium atom to the bipyridyl ligand, those of [4a](+)-[4c](+) contain LMCT bands originating on the acetylide ligands. This is in agreement with the IR and ESR spectra of [4a](+)-[4c](+). The X-ray crystal structures of the redox pair 4a and [4a][PF(6)()] have been determined, allowing the bonding within the metal-acetylide unit to be analyzed, and an attempt is made to determine Lever electrochemical parameters (E(L)) for the vinylidene and acetylide ligands seen herein. Room temperature luminescence measurements on 4a-c show that the compounds are not strongly emissive. 相似文献
17.
Seetharaman SK Chung MC Englich U Ruhlandt-Senge K Sponsler MB 《Inorganic chemistry》2007,46(2):561-567
The red, five-coordinate complexes Ru(CO)Cl(PPh(3))2(CH=CHPh) and [Ru(CO)Cl(PPh(3))2]2(mu-CH=CHC(6)H(4)CH=CH) undergo reversible coordination of PPh(3) at low temperature to produce the pale yellow, six-coordinate complexes Ru(CO)Cl(PPh(3))3(CH=CHPh) and [Ru(CO)Cl(PPh(3))3]2(mu-CH=CHC(6)H(4)CH=CH). X-ray crystal structures of the latter complex and of the hydride complex RuH(CO)Cl(PPh(3))3 were obtained. 1H and 31P NMR spectra between 20 and -70 degrees C exhibit large changes in both equilibrium constants and dynamic effects. Thermodynamic parameters, DeltaH = -17.5 +/- 2.0 kcal/mol and DeltaS = -57.5 +/- 7.6 eu, were obtained for PPh(3) coordination to the monoruthenium complex, and activation parameters, DeltaH = 20.6 +/- 0.7 kcal/mol and DeltaS = 41.6 +/- 2.0 eu, were obtained for the reverse decoordination. Coordination of PPh(3) was not observed upon cooling of the shorter bridged complex, [Ru(CO)Cl(PPh(3))2]2(mu-CH=CHCH=CH). 相似文献
18.
Wilton-Ely JD Honarkhah SJ Wang M Tocher DA Slawin AM 《Dalton transactions (Cambridge, England : 2003)》2005,(11):1930-1939
A series of vinyl, aryl, acetylide and silyl complexes [Ru(R)(kappa2-MI)(CO)(PPh3)2] (R = CH=CH2, CH=CHPh, CH=CHC6H4CH3-4, CH=CH(t)Bu, CH=2OH, C(C triple bond CPh)=CHPh, C6H5, C triple bond CPh, SiMe2OEt; MI = 1-methylimidazole-2-thiolate) were prepared from either [Ru(R)Cl(CO)(PPh3)2] or [Ru(R)Cl(CO)(BTD)(PPh3)2](BTD = 2,1,3-benzothiadiazole) by reaction with the nitrogen-sulfur mixed-donor ligand, 1-methyl-2-mercaptoimidazole (HMI), in the presence of base. In the same manner, [Os(CH=CHPh)(kappa2-MI)(CO)(PPh3)2] was prepared from [Os(CH=CHPh)(CO)Cl(BTD)(PPh3)2]. The in situ hydroruthenation of 1-ethynylcyclohexan-1-ol by [RuH(CO)Cl(BTD)(PPh3)2] and subsequent addition of the HMI ligand and excess sodium methoxide yielded the dehydrated 1,3-dienyl complex [Ru(CH=CHC6H9)(kappa2-MI)(CO)(PPh3)2]. Dehydration of the complex [Ru(CH=CHCPh2OH)(kappa2-MI)(CO)(PPh3)2] with HBF4 yielded the vinyl carbene [Ru(=CHCH=CPh2)(kappa2-MI)(CO)(PPh3)2]BF4. The hydride complexes [MH(kappa2-MI)(CO)(PPh3)2](M = Ru, Os) were obtained from the reaction of HMI and KOH with [RuHCl(CO)(PPh3)3] and [OsHCl(CO)(BTD)(PPh3)2], respectively. Reaction of [Ru(CH=CHC6H4CH3-4)(kappa2-MI)(CO)(PPh3)2] with excess HC triple bond CPh leads to isolation of the acetylide complex [Ru(C triple bond CPh)(kappa2-MI)(CO)(PPh3)2], which is also accessible by direct reaction of [Ru(C triple bond CPh)Cl(CO)(BTD)(PPh3)2] with 1-methyl-2-mercaptoimidazole and NaOMe. The thiocarbonyl complex [Ru(CPh = CHPh)Cl(CS)(PPh3)2] reacted with HMI and NaOMe without migration to yield [Ru(CPh= CHPh)(kappa2-MI)(CS)(PPh3)2], while treatment of [Ru(CH=CHPh)Cl(CO)2(PPh3)2] with HMI yielded the monodentate acyl product [Ru{eta(1)-C(=O)CH=CHPh}(kappa2-MI)(CO)(PPh3)2]. The single-crystal X-ray structures of five complexes bearing vinyl, aryl, acetylide and dienyl functionality are reported. 相似文献
19.
Churchill MR Keil KM Bright FV Pandey S Baker GA Keister JB 《Inorganic chemistry》2000,39(25):5807-5816
The complexes Ru(CO)2L2(AL-2H) (AL = alizarin; L = PPh3, PCyc3, PBu3, P(m-NaSO3C6H4)3), Ru(CO)(dppe)(PBu3)(AL-2H), and RuH(CO)L2(AL-H) (L = PPh3, PCyc3), and Ru(CO)2L2(AR-2H) (AR = anthrarobin; L = PBu3) were prepared by reactions of Ru3(CO)12, L, and AL, and the complexes RuH(CO)(PPh3)2(AL-H), RuH(CO)(PPh3)2(QN-H) (QN = quinizarin), and RuH(CO)(PPh3)2(LQN-H) (LQN = leucoquinizarin) are prepared by reactions of RuH2(CO)(PPh3)3 with AL or QN. The AL-2H and AR-2H ligands act as 1,2-catecholates, whereas the AL-H, QN-H, LQN-H ligands are 1,9-o-acylphenolate ligands. RuH(CO)(PPh3)2(AL-H) is characterized by X-ray crystallography. The electrochemistry of these complexes is examined, and the semiquinone complexes [Ru(CO)2L2(AL-2H)]+ (L = PPh3, PCyc3, PBu3) and [Ru(CO)(dppe)(PBu3)(AL-2H)]+ are generated by chemical oxidation and were characterized by EPR and IR spectroscopy. The photophysical properties are also reported. 相似文献
20.
Reaction of RuCl(2)(PPh(3))(3) with S(2)(-) sources yields a family of phosphine-containing Ru-S clusters which have been characterized crystallographically and by MALDI-MS. Ru(4)S(6)(PPh(3))(4) (Ru-Ru(av) = 2.94 A) has idealized T(d)() symmetry whereas Ru(6)S(8)(PPh(3))(6) (Ru-Ru(av) = 2.82 A) adopts the idealized O(h)() symmetry characteristic of Chevrel clusters. Ru(5)S(6)(PPh(3))(5) is formally derived by the addition of Ru(PPh(3)) to one face of Ru(4)S(6)(PPh(3))(4). In terms of its M-S connectivity, the Ru(5)S(6) cluster resembles a fragment of the FeMo cluster in nitrogenase. 相似文献