Synthesis and properties of five-co-ordinate complexes of ruthenium and osmium containing the bulky phosphine 1,2-bis(diisopropylphosphino)ethane (dippe). Crystal structure of [Ru(SPh)(dippe)2][BPh4 (original) (raw)
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Journal of Organometallic Chemistry, 2000
The 16-electron complex [(C 5 Me 5 )RuCl(PMe i Pr 2 )] (1) was obtained by reaction of [{(C 5 Me 5 )RuCl} 4 ] with PMe i Pr 2 in petroleum. This compound appears to be in equilibrium with the dimer [{(C 5 Me 5 )Ru(PMe i Pr 2 )} 2 (m-Cl) 2 ] as inferred from low-temperature NMR studies. The 18-electron complex [(C 5 Me 5 )RuCl(PMe i Pr 2 ) 2 ] was formed upon addition of PMe i Pr 2 to 1. The related species [(C 5 H 5 )RuCl(PMe i Pr 2 ) 2 ] (2) was obtained by reaction of [(C 5 H 5 )RuCl(PMe i Pr 2 )(PPh 3 )] with PMe i Pr 2 , followed by column chromatography. A range of Ru IV dihydrides [(C 5 R 5 )RuH 2 (PR 3 ) 2 ][BPh 4 ] (R=Me, H; PR 3 = PMe i Pr 2 , PEt 3 ) have been prepared and characterised. The corresponding monohydrido complexes [(C 5 R 5 )RuH(PR 3 ) 2 ] were obtained by deprotonation of the cationic dihydrides. Protonation at low temperature of either of these monohydrido complexes yielded back the corresponding dihydrido derivative, except in the case of [(C 5 Me 5 )RuH(PEt 3 ) 2 ], for which the metastable cationic dihydrogen complex [(C 5 Me 5 )Ru(H 2 )(PEt 3 ) 2 ] + was obtained and characterised by NMR spectroscopy. This compound rearranges to its dihydrido tautomer as the temperature is raised, and a kinetic study of such process was accomplished. Interestingly, the only isolable dinitrogen adduct of the type [(C 5 R 5 )Ru(N 2 )(PR 3 ) 2 ][BPh 4 ] among all possible combinations of phosphines and cyclopentadienyl ring substituents was [(C 5 Me 5 )Ru(N 2 )(PEt 3 ) 2 ][BPh 4 ].
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, 1998
Treatment of RuCl 2 (PPh 3 ) 3 and RuHCl(PPh 3 ) 3 with the tin compound CH 2 C(Me)CHC(Me)CH 2 SnMe 3 gives the corresponding acyclic pentadienyl halfsandwich (η 5 -CH 2 C(Me)CHC(Me)CH 2 )RuX(PPh 3 ) 2 [X = Cl, (2); H, ]. The steric congestion in 2 is most effectively relieved by formation of the cyclometalated complex (η 5 -CH 2 C(Me)CHC(Me)CH 2 )Ru(C 6 H 4 PPh 2 )(PPh 3 ) (4). Addition of 1 equiv of PHPh 2 to (η 5 -CH 2 CHCHCHCH 2 )RuCl(PPh 3 ) 2 (1) affords the chiral complex (η 5 -CH 2 CHCHCHCH 2 )RuCl(PPh 3 )(PHPh 2 ) (5), while compound (η 5 -CH 2 C-(Me)CHC(Me)CH 2 )RuCl(PPh 3 )(PHPh 2 )] (6) is directly obtained from the reaction of RuCl 2 (PPh 3 ) 3 with CH 2 C(Me)CHC(Me)CH 2 Sn(Me) 3 and PHPh 2 . Treatment of RuCl 2 (PPh 3 ) 3 with the corresponding Me 3 SnCH 2 CHCHCHNR (R = Cy, t-Bu) affords (1-3,5-η-CH 2 CHCHCHNCy)RuCl(PPh 3 ) 2 (7) and [1-3,5-η-CH 2 CHCHCHN-(t-Bu)]RuCl(PPh 3 ) 2 (8). The hydrolysis of 7, on a silica gel chromatography column, allows the isolation of RuCl(η 5 -CH 2 CHCHCHO)(PPh 3 ) 2 (9). The azapentadienyl complex 7 reacts with 1 equiv of PHPh 2 to afford [1-3,5-η-CH 2 CHCHCHN(Cy)]RuCl(PPh 3 )(PHPh 2 ) (10), while the corresponding product [1-3,5-η-CH 2 CHCHCHN(t-Bu)]RuCl(PPh 3 )(PHPh 2 ) (11) from 8 is only observed through 1 H and 31 P NMR spectroscopy as a mixture of isomers. Two equivalents of PHPh 2 gives spectroscopic evidence of [η 3 -CH 2 CHCHCHN(t-Bu)]-RuCl(PHPh 2 ) 3 . A mixture of products [η 5 -CH 2 C(Me)CHC Me)O]RuCl(PPh 3 ) 2 (12) and [η 5 -CH 2 C(Me)CHC(Me)O]RuH-(PPh 3 ) 2 (13) is obtained from reaction of RuCl 2 (PPh 3 ) 3 with Li[CH 2 C(Me)CHC(Me)O]. In contrast, the oxopentadienyl compound 13 is cleanly formed from RuHCl(PPh 3 ) 3 and Li[CH 2 C(Me)CHC(Me)O]. An attempt to separate compounds 12 and 13 by crystallization gives an orthometalated product [η 5 -CH 2 C(Me)CHC(Me)O]Ru(C 6 H 4 PPh 2 )(PPh 3 ) , which is the oxopentadienyl analogue to 4. The bulky [1-3,5-η-CH 2 C(t-Bu)CHC(t-Bu)O]RuH(PPh 3 ) 2 (15) analogue to 13 has also been prepared from RuHCl(PPh 3 ) 3 and Li[CH 2 C(t-Bu)CHC(t-Bu)O]. Compounds 3, 5, 6, 7, and 12−15 have been structurally characterized. The preferred heteropentadienyl orientations and the relative positions of the H, Cl, PPh 3 , and PHPh 2 ligands have been established in the piano-stool structures for all compounds, and it can be definitively surmised that the chemistry involved in the heteropentadienyl halfsandwich compounds studied is dominated by steric effects.
Inorganic Chemistry, 1990
Molecular hydrogen complexes [MH(q2-H2)P4]BF4 [M = Ru, Os; P = PhP(OEt),, P(OEt),, P(0Me)J were prepared by allowing the MH2P4 hydrides to react with HBF4.Et20 at -80 OC in ethanol or diethyl ether. Their characterization by variable-temperature IH and )'P NMR data, TI measurements, and JHD values is reported. The influence of the phosphite ligand and the central metal (Fe, Ru, Os) on the properties of the complexes is also discussed. Monohydrido complexes of the type [MHLP4]BPh4 [L = CO, 4-CH3C6H4NC, 4-CH3C6H4CN; P = PhP(OEt),, P(OEt),] were obtained by substitution of dihydrogen with the appropriate ligand. The reactions of arenediazonium cations with the molecular hydrogen and dihydride RuH2P4 complexes were examined, and the syntheses of pentacoordinate [Ru(ArN=NH)P4](BPh4), and [Ru(ArN2)P4]BPh4 complexes and octahedral [RuH-(ArN=NH)P,]BPh, and [Ru(ArN=NH),P4](BPh4), derivatives were achieved. The characterization of the complexes by IR and 'H and ''P N M R spectra is reported. (1) (a) Kubas, G. J.; Ryan, R. R.; Swanson, B. 1.; Vergamini, P. J.; Wasserman, H. J.
Polyhedron, 1995
Reaction of complexes [(q6C6Me6)RuC12] 2 and [(q5C5Me5)RhC12] 2 with the ligands L = Ph2PCH2PPh2 (dppm) or Ph2PCH2P(Se)Ph2 in benzene solutions led to neutral complexes with the general formula [(ring)MC12(r/IL)]. The reactivity of the uncoordinated P atom ofdppm has been studied. When the reaction was carried out in methanol solutions, cationic complexes, with the ligands acting in their bidentate form, were obtained. Similar cationic perchlorate complexes were prepared using acetone as solvent in the presence of sodium perchlorate, yielding [(ring)MCl(~/2L)]ClO4, where L=Ph2PCH2PPh2, PhzPCH2P(Se)Ph2 or PhzP(S)CHzP(S)Ph2. The complex [(r/6C6Me6)RuCI{qZ(SPPh)2 CH2-S,S'}]C104 reacted with sodium hydride in tetrahydrofuran or thallium pyrazolate in dichloromethane solution by deprotonation of the coordinated bidentate ligand giving the complex [(q6C6Me6)Ru{r/3(SPPhz)zCH-C,S,S'}]C104. The structure of this complex has been determined by single crystal X-ray diffraction methods. The complex contains a tridentate C,S,S'-bonded ligand occupying three coordination positions of a distorted octahedral ruthenium centre, with an q6C6Me 6 group completing the coordination sphere.
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.
Journal of Organometallic Chemistry, 2008
Several Ru(II) complexes (g 5 -C 5 H 4 CO 2 H)Ru(g 2 -L)I have been prepared by the hydrolysis of the ester linkage in (g 5 -C 5 H 4 CO 2t-Bu)Ru(g 2 -L)Cl with trimethylsilyl iodide. The hydrides (g 5 -C 5 H 4 CO 2 H)Ru(g 2 -L)H may be prepared by reduction of the iodide complexes in KOH/MeOH solutions followed by acidification. Complexes with several chelating bisphosphine ligands have been prepared in this way. The carboxylate anions [(g 5 -C 5 H 4 CO 2 )Ru(g 2 -L)H] À are readily protonated by weak acids to give the carboxyCp complexes. The pK a of the carboxy proton of (g 5 -C 5 H 4 CO 2 H)Ru(dppe)H (dppe = 1,2-bis(diphenylphosphino)ethane) is 11.3 in DMSO. Protonation of the neutral hydride complex (g 5 -C 5 H 4 CO 2 H)Ru(dppf)H gives the cationic dihydride (g 5 -C 5 H 4 CO 2 H)Ru(dppf)H + 2 ; the dihydride structure has been confirmed by measuring the T 1 of its 1 H NMR hydride resonance over a range of temperatures. The oxidations of the halide complexes (g 5 -C 5 H 4 CO 2 H)Ru(dppf)I and (g 5 -C 5 H 4 CO 2 t-Bu)Ru(dppf)Cl (dppf = 1,1 0 -bis(diphenylphosphino)ferrocene) have been studied by cyclic voltammetry.
Half-Sandwich Ruthenium-Phosphine Complexes with Pentadienyl and Oxo- and Azapentadienyl Ligands
Organometallics, 2012
Treatment of RuCl 2 (PPh 3 ) 3 and RuHCl(PPh 3 ) 3 with the tin compound CH 2 C(Me)CHC(Me)CH 2 SnMe 3 gives the corresponding acyclic pentadienyl halfsandwich (η 5 -CH 2 C(Me)CHC(Me)CH 2 )RuX(PPh 3 ) 2 [X = Cl, (2); H, ]. The steric congestion in 2 is most effectively relieved by formation of the cyclometalated complex (η 5 -CH 2 C(Me)CHC(Me)CH 2 )Ru(C 6 H 4 PPh 2 )(PPh 3 ) (4). Addition of 1 equiv of PHPh 2 to (η 5 -CH 2 CHCHCHCH 2 )RuCl(PPh 3 ) 2 (1) affords the chiral complex (η 5 -CH 2 CHCHCHCH 2 )RuCl(PPh 3 )(PHPh 2 ) (5), while compound (η 5 -CH 2 C-(Me)CHC(Me)CH 2 )RuCl(PPh 3 )(PHPh 2 )] (6) is directly obtained from the reaction of RuCl 2 (PPh 3 ) 3 with CH 2 C(Me)CHC(Me)CH 2 Sn(Me) 3 and PHPh 2 . Treatment of RuCl 2 (PPh 3 ) 3 with the corresponding Me 3 SnCH 2 CHCHCHNR (R = Cy, t-Bu) affords (1-3,5-η-CH 2 CHCHCHNCy)RuCl(PPh 3 ) 2 (7) and [1-3,5-η-CH 2 CHCHCHN-(t-Bu)]RuCl(PPh 3 ) 2 (8). The hydrolysis of 7, on a silica gel chromatography column, allows the isolation of RuCl(η 5 -CH 2 CHCHCHO)(PPh 3 ) 2 (9). The azapentadienyl complex 7 reacts with 1 equiv of PHPh 2 to afford [1-3,5-η-CH 2 CHCHCHN(Cy)]RuCl(PPh 3 )(PHPh 2 ) (10), while the corresponding product [1-3,5-η-CH 2 CHCHCHN(t-Bu)]RuCl(PPh 3 )(PHPh 2 ) (11) from 8 is only observed through 1 H and 31 P NMR spectroscopy as a mixture of isomers. Two equivalents of PHPh 2 gives spectroscopic evidence of [η 3 -CH 2 CHCHCHN(t-Bu)]-RuCl(PHPh 2 ) 3 . A mixture of products [η 5 -CH 2 C(Me)CHC Me)O]RuCl(PPh 3 ) 2 (12) and [η 5 -CH 2 C(Me)CHC(Me)O]RuH-(PPh 3 ) 2 (13) is obtained from reaction of RuCl 2 (PPh 3 ) 3 with Li[CH 2 C(Me)CHC(Me)O]. In contrast, the oxopentadienyl compound 13 is cleanly formed from RuHCl(PPh 3 ) 3 and Li[CH 2 C(Me)CHC(Me)O]. An attempt to separate compounds 12 and 13 by crystallization gives an orthometalated product [η 5 -CH 2 C(Me)CHC(Me)O]Ru(C 6 H 4 PPh 2 )(PPh 3 ) , which is the oxopentadienyl analogue to 4. The bulky [1-3,5-η-CH 2 C(t-Bu)CHC(t-Bu)O]RuH(PPh 3 ) 2 (15) analogue to 13 has also been prepared from RuHCl(PPh 3 ) 3 and Li[CH 2 C(t-Bu)CHC(t-Bu)O]. Compounds 3, 5, 6, 7, and 12−15 have been structurally characterized. The preferred heteropentadienyl orientations and the relative positions of the H, Cl, PPh 3 , and PHPh 2 ligands have been established in the piano-stool structures for all compounds, and it can be definitively surmised that the chemistry involved in the heteropentadienyl halfsandwich compounds studied is dominated by steric effects.