Facile substitution of triphenylphosphine in Wilkinson's catalyst by Sn(N-tert-Bu)2SiMe2. Syntheses and molecular structures of square-planar and homoleptic trigonal-bipyramidal stannylene complexes of rhodium(I) (original) (raw)
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Dalton Transactions, 2007
Two equivalents of Ph 2 PC≡CR (R = H, Me, Ph) react with thf solutions of cis-[Ru(acac) 2 (g 2-alkene) 2 ] (acac = acetylacetonato; alkene = C 2 H 4 , 1; C 8 H 14 , 2) at room temperature to yield the orange, air-stable compounds trans-[Ru(acac) 2 (Ph 2 PC≡CR) 2 ] (R = H, trans-3; Me = trans-4; Ph, trans-5) in isolated yields of 60-98%. In refluxing chlorobenzene, trans-4 and trans-5 are converted into the yellow, air-stable compounds cis-[Ru(acac) 2 (Ph 2 PC≡CR) 2 ] (R = Me, cis-4; Ph, cis-5), isolated in yields of ca. 65%. From the reaction of two equivalents of Ph 2 PC≡CPPh 2 with a thf solution of 2 an almost insoluble orange solid is formed, which is believed to be trans-[Ru(acac) 2 (l-Ph 2 PC≡CPPh 2)] n (trans-6). In refluxing chlorobenzene, the latter forms the air-stable, yellow, binuclear compound cis-[{Ru(acac) 2 (l-Ph 2 PC≡CPPh 2)} 2 ] (cis-6). Electrochemical studies indicate that cis-4 and cis-5 are harder to oxidise by ca. 300 mV than the corresponding trans-isomers and harder to oxidise by 80-120 mV than cis-[Ru(acac) 2 L 2 ] (L = PPh 3 , PPh 2 Me). Electrochemical studies of cis-6 show two reversible Ru II/III oxidation processes separated by 300 mV, the estimated comproportionation constant (K c) for the equilibrium cis-6 2+ + cis-6 2(cis-6 +) being ca. 10 5. However, UV-Vis spectra of cis-6 + and cis-6 2+ , generated electrochemically at −50 • C, indicate that cis-6 + is a Robin-Day Class II mixed-valence system. Addition of one equivalent of AgPF 6 to trans-3 and trans-4 forms the green air-stable complexes trans-3•PF 6 and trans-4•PF 6 , respectively, almost quantitatively. The structures of trans-4, cis-4, trans-4•PF 6 and cis-6 have been confirmed by X-ray crystallography.
Diphosphinito-bridged ruthenium(II) and rhodium(III) complexes with stereogenic metal centers
Inorganica Chimica Acta, 1999
The bis-4-phosphinito ligands [(p-Ph 2 POC 6 H 4) 2 X] (X=O, 1; X= CMe 2 , 2; X= S, 3) react with [Ru(h 6-p-cymene)Cl 2 ] 2 to form the binuclear complexes {[Ru(h 6-p-cymene)Cl 2 ] 2 [m-(p-Ph 2 POC 6 H 4) 2 X]} (X =O, 4; X= CMe 2 , 5; X=S, 6) in good yields as red air stable solids. The crystal structures of 4-6 were determined by X-ray analysis. In acetonitrile and in the presence of AgPF 6 (1:1 equiv. with respect to Ru), complexes 4-6 undergo substitution to yield the cationic complexes {[Ru(h 6-pcymene)Cl(CH 3 CN)] 2 [m-(p-Ph 2 POC 6 H 4) 2 X]}[PF 6 ] 2 (X= O, 7; X= CMe 2 , 8; X=S, 9), whose stability in solution is very limited. The acetonitrile ligand in complexes 7-9 can be easily replaced by carbon monoxide; the products {[Ru(h 6-p-cymene)Cl(CO)] 2 [m-(p-Ph 2 POC 6 H 4) 2 X]}[PF 6 ] 2 (X=O, 10; X=CMe 2 , 11; X=S, 12) can only be detected in solution under a CO atmosphere and have limited stability. The reaction of [Rh(h 5-C 5 Me 5)Cl 2 ] 2 with ligands 1-3 results in the formation of the complexes {[Rh(h 5-C 5 Me 5)Cl 2 ] 2 [m-(p-Ph 2 POC 6 H 4) 2 X]} (X =O, 13; X=CMe 2 , 14; X= S, 15), which have been isolated as red-orange air stable solids. The cationic complexes {[Rh(h 5-C 5 Me 5)Cl(CH 3 CN)] 2 [m-(p-Ph 2 POC 6 H 4) 2 X]}[PF 6 ] 2 (X =O, 16; X= CMe 2 , 17; X=S, 18), in which the metal atoms are stereogenic centers, have been obtained from the corresponding complexes 13-15, by treatment in CH 3 CN with AgPF 6 , and have been characterized only in solution by 31 P{ 1 H} NMR spectra and conductivity measurements. On reaction with ligands 1-3, [Rh(h 5-C 5 H 5)(CO) 2 ] was converted into the binuclear phosphinito-bridged complexes {[Rh(h 5-C 5 H 5)(CO)] 2 [m-(p-Ph 2 POC 6 H 4) 2 X]} (X=O, 19; X= CMe 2 , 20; X= S, 21). The reactions of the binuclear complex {[Rh(h 5-C 5 H 5)(CO)] 2 [m-(p-Ph 2 POC 6 H 4) 2 S]} (21) with CH 3 I, S-(+)-1-bromo-2-methylbutane and racemic PhCH(CH 3)Br were also studied. The products were the corresponding acyl derivatives. The reaction of 21 with neat CH 3 I easily afforded the complex {[Rh(h 5-C 5 H 5)(COCH 3)I] 2 [m-(p-Ph 2 POC 6 H 4) 2 S]} (23), whose structural determination by X-ray analysis is also reported.
Organometallics, 1990
Pyrolysis of Ru,(CO),,,(dppf) (cyclohexane, 81 "C, 2 h) gave six major products, of which the title complexes were fully characterized by X-ray crystallographic studies. Structural features include metalated 7'-and p-71,72-C6H4 groups, p3-71,7',72-and ~(~-~~,~~,~~,~~-b e n z y n e ligands, and a metalated ferrocene nucleus that further interacts with an Ru, cluster via a direct Fe-Ru donor bond. These complexes are formed by reactions involving addition of C-H bonds to clusters, C-H, P-(C5 ring), and P-(c6 ring) bond cleavage, and migration of H to C5 ring carbons to give ferrocenyl (Fe(q-C5H4)(q-C5H5)) groups. Crystal data are as follows.
Organometallics, 1989
The reaction of bis(dimethy1phosphino)methane with R u~( C O )~~ under CO pressure at 120 "C leads to the quantitative formation of the binuclear ruthenium complex R~, ( d m p m )~( C O )~ Although this complex was previously unreported, the s ectroscopic data and X-ray crystallographic analysis [ P l space group, a = 10.569 (2) A, b = 11.964 (2) i, c = 12.232 (4) A, LY = 77.22 (2)O, = 77.53 (3)O, y = 75.14 (3)O, V = 1437 (1) A3, 2 = 21 show that it has a structure analogous to that found for related bmucleatmg diphosphines. The reaction of R~~( d m p m ) , ( C O )~ with acids such as HBF4 occurs rapidly and leads t o quantitative protonation of the metal-metal bond forming [HRuz(dmpm),(CO),]BF4. The reaction with diphenylacetylene occurs at 90 "C in toluene leading t o R U~(~~~~)~( C O )~( C~H & C C~H~) , which was shown to contain a az-bridging acetylene ligand by X-ray crystallograph [m1/a space group, a = 13.140 (3) A, b = 15.157 (4) A, c = 16.280 (3) A, p = 92.56 (2)O, V = 3239 (2) i3, 2 = 41. Although the analogous product can be isolated by treating R~~( d m p m )~( C O )~ c2 c10 m A. Ligand-Metal-Ligand C(ll)-R~(l)-C(l2) 100.6 (2) C(22)-Ru(2)-C(21) 101.4 (2) C(ll)-Ru(l)-C(OA) 99.8 (2) C(22)-Ru(2)-C(OB) 99.3 (2) C(ll)-R~(l)-P(l2) 88.6 (2) C(22)-Ru(Z)-P(22) 90.8 (2) C(ll)-Ru(l)-P(ll) 90.2 (2) C(22)-Ru(2)-P(21) 88.0 (2) C (1 l)-Ru( l)-Ru(2) 167.3 (1) C (22)-Ru(2)-Ru( 1) 167.1 (2) C(12)-Ru(l)-C(OA) 159.3 (2) C(2l)-Ru(2)-C(OB) 159.0 (2) C(12)-Ru(l)-P(12) 92.6 (2) C(2l)-Ru(Z)-P(22) 91.8 (2) C(l2)-R~(l)-P(ll) 91.9 (2) C(21)-Ru(2)-P(21) 93.4 (2) C(12)-Ru(l)-Ru(2) 91.8 (2) C(21)-Ru(Z)-Ru(l) 91.3 (2) C(OA)-Ru(l)-P(12) 84.5 (1) C(OB)-Ru(2)-P(22) 91.4 (1) C(OA)-Ru(l)-P(ll) 91.4 (1) C(OB)-Ru(2)-P(21) 83.8 (1) C(OA)-Ru(l)-Ru(2) 68.1 (1) C(OB)-Ru(2)-Ru(l) 68.2 (1) P(l2)-R~(l)-P(ll) 175.49 (5) P(22)-Ru(2)-P(21) 174.84 (5) P(12)-Ru(l)-Ru(2) 93.75 (4) P(22)-Ru(2)-Ru(l) 86.52 (4) P(ll)-Ru(l)-Ru(2) 86.53 (4) P(21)-Ru(2)-Ru(l) 93.55 (4) B. Metal Carbonyls and Other Ligands Ru(l)-P(ll)-C(l) 116.1 (2) Ru(2)-P(21)-C(l) 114.1 (2) Ru(l)-P(12)-C(2) 114.2 (2) Ru(2)-P(22)-C(2) 116.4 (2) Ru(l)-C(ll)-O(ll) 177.3 (5) Ru(2)-C(22)-0(22) 177.2 (4) R~(l)-C(12)-0(12) 177.7 (5) Ru(2)-C(21)-0(21) 178.7 (5) Ru(l)-C(OA)-C(OB) 112.2 (3) Ru(2)-C(OB)-C(OA) 111.5 (3) Ru(l)-C(OA)-C(lA) 125.5 (3) Ru(2)-C(OB)-C(lB) 124.4 (3) C(lA)-C(OA)-C(OB) 122.3 (4) C(1B)-C(0B)-C(0A) 124.0 (4) P(ll)-C(l)-P(21) 109.9 (2) P(12)-C(2)-P(22) 110.5 (2)
Organometallics, 2004
Novel organometallic [Ru(PCP)(tpy)]Cl complexes, containing the terdentate coordinating monoanionic bisphosphinoaryl ligands [C 6 H 3 (CH 2 PR 2 ) 2 -2,6] -(PCP) (R ) Ph (11); iPr (12)) and 2,2′:6′,2′′-terpyridine, have been synthesized by two different synthetic pathways in good yields. The molecular structure in the solid state of [Ru{C 6 H 2 (CH 2 PPh 2 ) 2 -2,6}(tpy)](OTf) (14) has been determined by X-ray crystallography. The spectroscopic and electrochemical properties of the [Ru(PCP)(tpy)]Cl complexes were compared with those obtained for [Ru{C 6 H 3 (CH 2 NMe 2 ) 2 -2,6}(tpy)](Cl) (3) containing the monoanionic bisaminoaryl ligand [C 6 H 3 (CH 2 NMe 2 ) 2 -2,6] -(NCN). The obtained results revealed that substitution of the NCNpincer ligand by PCP-pincer ligands offers a powerful tool to tune the redox and photophysical properties as well as the reactivity of the ruthenium(II) metal centers in the resulting photoactive monomeric species. . (1) (a) Sauvage, J.-P.; Collin, J.-P.; Chambron, J.-C.; Guillerez, S.; Coudret, C.; Balzani, V.; Barigelletti, F.; De Cola, L.; Flamigni, L. Lloris, J. M.; Martínez-Máñ ez, R.; Benito, A.; Soto, J.; Pardo, T.; Miranda, M. A.; Markos, M. D. Eur. J. Inorg. Chem. 2000, 741. (g) Constable, E. C.; Housecroft, C. E.; Johnston, L. A.; Armspach, D.; Neuburger, M.; Zehnder, M. Polyhedron 2001, 20, 483. (h) Maestri, M.; Armaroli, N.; Balzani, V.; Constable, E. C.; Cargill Thompson, A. M. W. Inorg. Chem. 1995Chem. , 34, 2759 (2) Juris, A.; Balzani, V.; Barigelletti, F.; Campagna, S.; Belser, P.; von Zelensky, A. Coord. Chem. Rev. 1998, 84, 85. (3) (a) Hissel, M.; El-Ghayoury, A.; Harriman, A.; Ziessel, R. Angew. (5) (a) Padilla-Tosta, M. E.; Lloris, J. M.; Martínez-Máñ ez, Pardo, T.; Soto, J.; Benito, A.; Markos, M. D. Inorg. Chem. Commun. 2000, 3, 45. (b) Beley, M.; Collin, J.-P.; Sauvage, J.-P. Inorg. Chem. 1993, 32, 4539. (c) Collin, J.-P.; Gaviñ a, P.; Heitz, V.; Sauvage, J.-P Eur.
Synthesis, spectral, and redox properties of three triply bridged complexes of ruthenium
Inorganic Chemistry, 1989
Syntheses are described for the ligand-bridged complexes [(tpm)Ru"'(p-O)(p-L),Ru"'(tpm)"+ (L = 02P(0)(OH), n = 0 (1); L = 0 2 C 0 , n = 0 (2); L = 02CCH3, n = 2 (3); tpm is the tridentate, facial ligand tris(1-pyrazoly1)methane. The X-ray crystal structure of [(tpm)Ru(p-O)(p-O2P(O)(0H)),Ru(tpm)].8H2O was determined from three-dimensional X-ray counter data. The com lex crystallizes in the trigonal space group P3221 with three molecules in a cell of dimensions (I = 18.759 (4) A and c = 9.970 ( 6 ) 1. The structure was refined to a weighted R factor of 0.042 based on 1480 independent reflections with I 1 3 4 . The structure reveals that the complex consists of two six-coordinate ruthenium atoms that are joined by a p-oxo bridge (rRu4 = 1.87 A; LRuORu = 1 2 4 . 6 O ) and two p-hydrogen phosphato bridges (average rRu+ = 2.07 A) which are capped by two tpm ligands.
Dalton Transactions, 2007
Two equivalents of Ph 2 PC≡CR (R = H, Me, Ph) react with thf solutions of cis-[Ru(acac) 2 (g 2-alkene) 2 ] (acac = acetylacetonato; alkene = C 2 H 4 , 1; C 8 H 14 , 2) at room temperature to yield the orange, air-stable compounds trans-[Ru(acac) 2 (Ph 2 PC≡CR) 2 ] (R = H, trans-3; Me = trans-4; Ph, trans-5) in isolated yields of 60-98%. In refluxing chlorobenzene, trans-4 and trans-5 are converted into the yellow, air-stable compounds cis-[Ru(acac) 2 (Ph 2 PC≡CR) 2 ] (R = Me, cis-4; Ph, cis-5), isolated in yields of ca. 65%. From the reaction of two equivalents of Ph 2 PC≡CPPh 2 with a thf solution of 2 an almost insoluble orange solid is formed, which is believed to be trans-[Ru(acac) 2 (l-Ph 2 PC≡CPPh 2)] n (trans-6). In refluxing chlorobenzene, the latter forms the air-stable, yellow, binuclear compound cis-[{Ru(acac) 2 (l-Ph 2 PC≡CPPh 2)} 2 ] (cis-6). Electrochemical studies indicate that cis-4 and cis-5 are harder to oxidise by ca. 300 mV than the corresponding trans-isomers and harder to oxidise by 80-120 mV than cis-[Ru(acac) 2 L 2 ] (L = PPh 3 , PPh 2 Me). Electrochemical studies of cis-6 show two reversible Ru II/III oxidation processes separated by 300 mV, the estimated comproportionation constant (K c) for the equilibrium cis-6 2+ + cis-6 2(cis-6 +) being ca. 10 5. However, UV-Vis spectra of cis-6 + and cis-6 2+ , generated electrochemically at −50 • C, indicate that cis-6 + is a Robin-Day Class II mixed-valence system. Addition of one equivalent of AgPF 6 to trans-3 and trans-4 forms the green air-stable complexes trans-3•PF 6 and trans-4•PF 6 , respectively, almost quantitatively. The structures of trans-4, cis-4, trans-4•PF 6 and cis-6 have been confirmed by X-ray crystallography.