Mark G. Humphrey

Cluster chemistry: XXXXVIII. Some reactions of Ru3(CO)12 with nitrogen heterocycles. X-ray crystal structures of Ru3(μ-CO)2(CO)8(bipy) and Ru3(μ-H){μ-N2C3H(CF3)2-3,5}(CO)10

Abstract Reactions between Ru 3 (CO) 12 and the nitrogen heterocycles pyridine, 2,2′-bi-pyridyl, pyrazole, 3,5-dimethylpyrazole and 3,5-bis(trifluoromethyl)pyrazole are described. Pyridine afforded the cyclometallated complex Ru 3 (μ-H)(μ-NC 5 H 4 )(CO) 10 , which with excess pyridine formed Ru 3 (μ-H) 2 (μ-NC 5 H 4 ) 2 (CO) 8 . 2,2′-Bipyridyl gave purple Ru 3 (μ-CO) 2 (CO) 8 (bipy), shown by an X-ray structure to have an Fe 3 (CO) 12 -type structure, with the bipy chelating one of the CO-bridged Ru atoms. The pyrazoles gave Ru 3 (μ-H)(μ-N 2 CP 3 HR 2 )(CO) 10 (R = H, Me or CF 3 ), in which the pyrazolide ligand spans an Ruue5f8Ru bond also bridged by H, as shown by the X-ray structure of the CF 3 derivative. The bipyridyl and pyrazole complexes both crystallise in the monoclinic system, the former in space group P 2 1 / n with unit cell dimensions a 7.834(2), b 25.818(2), c 11.717(1) A, β 107.41(1)° with Z = 4 and the latter in space group P 2 1 / c , unit cell dimensions a 16.802(3), b 7.726(1), c 18.807(3) A, β 114.24(1)° with Z = 4. The structures were refined by conventional least-squares methods with the use of 3336 (2993 for the pyrazole structure) reflections with I > 2.5σ( I ) to final R = 0.031 and R w = 0.034 (0.025 and 0.026).

Cyclopentadienyl-ruthenium and -osmium chemistry: XXVII. X-ray structures of Ru(CCPh)(dppe)(η-C5H5) and of [Ru(L)(PPh3)2(η-C5H5)]X (L = C(OMe)Et, X = PF6; L = CCMePh, X = I)☆

Determinations of the crystal structures of the acetylide Ru(Cue5fcCPh)(dppe)(η-C5H5), the vinylidene [Ru(Cue5fbCMePh)(PPh3)2(η-C5H5)]I and the carbene [Ru{C(OMe)Et}(PPh3)2(η-C5H5)][PF6], have enabled comparison of the Ruue5f8C(α) bonds in these and a number of related complexes. Cationic complexes have Ruue5f8C bonds shorter (by 0.05–0.1 A) than values expected on the basis of normal covalent radii, but in the case of vinyl and acetylide complexes there does not appear to be any significant shortening of the Ruue5f8C bond which can be ascribed to back-bonding from the metal to the unsaturated carbon-bonded ligand. Ru(Cue5fcCPh)(dppe)(η-C5H5) crystallises in the monoclinic space group P21/n, with a 14.642(4), b 14.018(3), c 16.490(4) A, β 105.08(2)°, Z 4; [Ru(Cue5fbCMePh)(PPh3)2(η-C5H5)]I crystallises in the orthorhombic space group P212121, a 12.612(4), b 15.607(3), c 22.357(6) A, Z 4; [Ru{C(OMe)Et}(PPh3)2(η-C5H5)][PF6 crystallises in the orthorhombic space group P212121, a 11.999(3), b 14.948(1), c 22.342(3) A, Z 4. For 4841, 2614 and 3299 data (I > 2.5σ(I), respectively, refinements converged with R, Rw values of 0.038 and 0.048, 0.047 and 0.053, and 0.040 and 0.044 for the three complexes.

RUTHENIUM CLUSTERS CONTAINING N-DONOR LIGANDS

Presentation dune serie de complexes carbonyles du ruthenium avec des coordinats heterocycliques azotes aromatiques: reactivite chimique et structure. Synthese bibliographique

Cyclopentadienyl-ruthenium and -osmium chemistry. XXV: Conversion of alkoxycarbene complexes to vinyl ether derivatives: X-ray structure of Ru{C(OPri)=CHPh}(CO)(PPh3)(η-C5H5)

Abstract Several cationic alkoxy(alkyl)carbene complexes containing the Ru(L)(PPh 3 )(η-C 5 H 5 ) (L = CO or PPh 3 ) moiety have been deprotonated with NaOMe to the corresponding vinyl ether derivatives. The reaction is reversed by addition of HPF 6 . Many of the vinyl ether complexes were obtained as mixtures of E and Z isomers; the X-ray structure of Ru{;C(OPr 1 )ue5fbCHPh}(CO)(PPh 3 )(η-C 5 H 5 ) shows that it is obtained only as the E isomer, and that the unit cell contains equal numbers of the two enantiomers. Ru{;C(OPr 1 )ue5fbCHPh};(CO)(PPh 3 )(η-C 5 H 5 ) is monoclinic, space group P 2 1 / c , with a 10.337(5), b 15.161(4), c 18.714(5) A, β 90.83(3)°, and Z = 4; 2240 reflections [ I > 2.5σ( I )] were refined to R = 0.0388, R w = 0.0436. Important distances: Ruue5f8C(vinyl) 2.103(6), Ruue5f8CO 1.832(7), Ruue5f8P 2.298(2), Cue5fbC(vinyl) 1.335(8), Cue5f8OMe 1.381(7) A. Addition of NaOMe to the product of the reaction between RuCl(PPh 3 ) 2 (η-C 5 H 5 ) and HCue5fcCC(O)Me in MeOH afforded a mixture of Ru{;Cue5fcCC(O)Me};(PPh 3 )(η-C 5 H 5 ) and Ru{;C(OMe)ue5fbCHC(O)Me};(PPh 3 ) 2 (η-C 5 H 5 ). The latter loses PPh 3 on standing in solution at ambient temperatures, forming the chelate complex Ru{;C(OMe)ue5fbCHC(O) Me};(PPh 3 )(η-C 5 H 5 ). The similar conversion of Ru{;C(OMe)ue5fbCHC(O)OMe};(PPh 3 ) 2 (η-C 5 H 5 ) to the corresponding chelate complex required heating at 65°C for 75 minutes.

Cyclopentadienyl-ruthenium and -osmium chemistry: XXVIII. Reactions and isomerisation of 1,2-bis(methoxycarbonyl)ethenyl complexes: X-ray structures of Ru{Z)-C(CO2Me)CH(CO2Me)} -(CO)(PPh3)(η-C5H5) · 0.5EtOH, Ru{(E)-C(CO2Me)CH(CO2Me)}(dppe)(η-C5H5) and Ru{C(CO2Me)C(CO2Me)C(CO2Me)CH(CO2Me)} - (PPh3)(η-C5H5)☆

A reinvestigation of the reaction between C2(CO2Me)2 and RuH(PPh3)2(η-C5H5) and some related complexes is reported. Initial cis addition is followed by conversion into the trans isomer. In the case of the bis-(PPh3) complex, isomerisation is followed by chelation of the ester CO group with concomitant displacement of one PPh3ligand. The resulting chelate complex reacts with CO or CNBut to give the (Z)-RuC(CO2Me)ue5fbCH(CO2Me) complexes; the (E)-isomer of the carbonyl complex is obtained by addition of C2(CO2Me)2to RuH(CO)(PPh3)(η-C5H5). The 1Hand 13C NMR spectra are not a reliable guide to assignment of the stereochemistry of the vinyl group. Other products isolated from the initial reaction are the bis-insertion product Ru{C(CO2Me)ue5fbC(CO2Me)C(CO2Me)ue5fbCH(CO2Me)} -(PPh3)(η-C5H5) and the 1/2 PPh3/C2(CO2Me)2 adduct. The molecular structures of Ru{(Z)-C(CO2Me)ue5fbCH(CO2Me)}(CO)(PPh3(η-C5H5) · 0.5EtOH, Ru{(E)-C(C2Me)ue5fbCH(CO2Me)}(dppe)(η-C5H5) and Ru{C(CO2Me)ue5fbC(CO2Me)C(CO2-Me)ue5fbCH(CO2Me)}(PPh3)(η-C5H5) have been determined. The cis isomer is monoclinic, space group P21,with a 9.328(8), b 17.385(10), c 10.356(7) A, β 101.78(3)° and Z = 2; 2107 data with I ≥ 2.5σ(I) were refined to R = 0.076 Rw = 0.085. The trans isomer is triclinic, space group P1, with a 10.404(7) b 11.221(6), c 13.230(9) A, α 92.67(5), β 110.56(5), γ 106.21(5)° and Z = 2; 2520 data with I ≥ 2.5σ(I) were refined to R = 0.055 Rw = 0.068. The butadienyl complex is monoclinic, space group P21/a, with a 19.655(8), b 8.674(4), c 21.060(5) A, β 116.22(3)° and Z = 4; 2724 data with I ≥ 2.5σ(I) were refined to R = 0.042, Rw = 0.047.

Cluster chemistry: LIII. Preparation and some substitution reactions of bis(arylimido)triruthenium complexes: X-ray structures of Ru3(μ 3-NPh) (μ3-NC6 H4 F-3) (CO)9 and Ru3(μ3-NPh)2(CO)8(L) (L = CNC6H3Me2-2,6 and PPh3)

Abstract Azoarenes, ArNue5fbNAr′, react with Ru3(CO)12 to give Ru3(μ3-NAr)(μ3- NAr′)(CO)9 (Ar = Ph, Ar′ = Ph, C6H4Me-3, C6H4CF3-3, C6H4F-3 (11), C6H4F-4; Ar = Ar′= C6H4Me-3) in moderate yields; for Ar = Ar′= Ph or C6H4Me-3, the mononuclear cyclometallated Ru(C6H3RNue5fbNC6H4R-3)2(CO)2 (R = H or Me) were also obtained in low yield. Fe3(CO)12 and azobenzene afford Fe3(μ3-NPh)2(CO)9 in very low yield. An X-ray study of 11 confirms the structural assignments made on the basis of the spectroscopic measurements: an Ru3 triangle with a non-bonded Ru…Ru vector is capped on both sides by a μ3-arylimido moiety. Electron transfer-catalysed reactions with isocyanides, tertiary phosphines and phosphites proceed to give CO-substituted products in moderate yields: complexes Ru3(μ3- NPh)2(CO)8(L) (L = CNC6H3Me2-2,6 (15), PPh3 (16), P(OMe)3), {Ru3(μ3- NPh)2(CO)8}2(μ-(PPh2)2C2) and Ru3(μ3-NPh)2(μ-LL)(CO)7 (LL = dppm, dppe) were obtained. X-ray structural studies of 15 and 16 show that the isocyanide ligand occupies an axial position, whereas the tertiary phosphine takes up an equatorial position, both on a terminal ruthenium atom. Crystals of 11, 15 and 16 crystallize in the monoclinic system with space group P21/n, a 11.496(2), b 14.020(2), c 15.735(2) A, β 99.43(1)°, Z=4 for 11; space group P21/n, a 11.933(2), b 18.952(2), c 14.370(4) A, β 100.29(2)°, Z=4 for 15; and space group Pc, a 17.507(3), b 11.657(2), c 19.518(4) A, β 100.41(2)°, Z = 4 for 16. The structures were refined by least-squares methods and at convergence R = 0.037, Rw= 0.048 for 3653 statistically significant reflections for 11; R = 0.041, Rw = 0.046 for 3903 reflections for 15; and R = 0.039, Rw= 0.047 for 5291 reflections for 16.

Reactions of transition metal σ-acetylide complexes: IX. Preparation and properties of some cycloheptatrienylvinylidene complexes

Abstract Addition of [C7H7][PF6] to iron, ruthenium or osmium alkynyl complexes has given eight cationic cycloheptatrienylvinylidene derivatives [M{C ue5fbC(C7H7)R}(L)2 (η-C5H5)][PF6] (M = Fe, Ru or Os; R = Me, Pr, Ph or C6F5; L = PPh3, L2 = dppm or dppe; but not all combinations). With Fe(C2Ph)(CO)2(η-C5H5), only [Fe(CO)2(thf)(η-C5H5)][PF6] was obtained. Reactions of the new complexes are characterised by loss of the C7H7 group. The NMR spectra and FAB mass spectra are described in detail.

Reactions of transition metal σ-acetylides: VIII. Preparation and properties of some aryldiazo-vinylidene complexes☆

Abstract Fourteen aryldiazovinylidene complexes of ruthenium and osmium have been made by addition of aryldiazonium cations to the appropriate σ-acetylides. Their properties and spectra (including FAB-MS) are described, and reactions with MeOH, hydride and methoxide are reported. Addition to and protonation, alkylation, and cyclomanganation of the aryldiazo functions are also described.

Cyclopentadienyl-ruthenium and -osmium chemistry: XXIX. The effect of chelation on Ru-C(sp2) bond lengths: X-ray structures of Ru(C6H4PPh2)(PPh3)(η-C5H5)-·0.5CH2Cl2 and Ru{C(CMePh)CH(PPh2)CH2PPh2}-(η-C5H5)☆

Abstract The molecular structures Ru(C 6 H 4 P Ph2)(PPh3)(η-C5H5) (1) and Ru{C(ue5fbCMe-Ph)CH(PPh 2 )CH 2 P Ph2}(η-C5H5) (2) have been determined. In 1, strain about the RuPCC chelate ring is accommodated largely by contraction of the intra-ring angles about the relevant atoms. In 2 there are similar contractions, together with marked lengthening of the Ru-C(sp2) bond (to 2.149(5) A) and of the Cue5f8C bond (1.534(7) A) from the vinyl α-carbon to the CHPPh2 group of the chelating tertiary phosphine; the latter bond is 0.11 A shorter than that in the iron analogue. Crystal data: 1 (as 0.5CH2Cl2 solvate): triclinic, space group P 1 , a 8.409(2), b 19.055(5), c 21.921(9) A, α 94.10(3), β 97.02(2), γ 99.92(2)°, U 3418.6 A3, Z = 4; 2007 data (I ≥ 2.5σ(I)) were refined to R = 0.047, Rw = 0.051; 2: triclinic, space group P 1 ,a 12.141(1), b 14.004(1), c 11.333(1) A, α 112.19(1), β 101.15(1), γ 69.01(1)°, U 1662.0 A3, Z = 2, 3788 data (I ≥ 2.5σ(I)) were refined to R = 0.047, Rw = 0.050.

Reactions of transition metal σ-acetylide complexes: III. Synthesis of some aryldiazovinylidene and cycloheptatrienylvinylidene complexes. X-ray structures of [Ru(CCPhNNC6H3Me2-3,4)(PPh3)2(η-C5H5)][BF4] · 0.67CH2Cl2 and [Ru{CCPh(C7H7)}(DPPE)(η-C5H5)][PF6] · 0.63CH2Cl2☆

Addition of arenediazonium or tropylium salts to Ru(C2Ph)(L)2(η-C5H5) (L2 = (PPh3)2 or DPPE) gives the corresponding cationic aryldiazovinylidene and cycloheptatrienylvinylidene complexes, respectively; the X-ray structures of the title complexes confirm the presence of the new ligands. The Ruue5f8C and Cue5fbC distances are 1.823(9) and 1.34(1) A for the aryldiazo complex, and 1.848(9) and 1.32(1) A for the cycloheptatrienyl derivative.