Michael R. Snow

Cluster chemistry : X. Preparation of 1,2-bis(diphenylphosphino)ethane derivatives of Ru3(CO)12: crystal and molecular structures of Ru3(CO)10(η-PH2PCH2CH2PPh2)

The reactions of dppe with Ru3(CO)12 catalysed by Ph2CO??? have been investigated. Under the appropriate conditions Ru3(CO)11(PPh2CH2CH2PPh2) (with only one P atom coordinated), [Ru3(CO)11]2(η-dppe) (with one dppe ligand bridging two Ru3(CO)11 clusters), Ru3(CO)10(η-dppe) and Ru3(CO)8(η-dppe)2(both with dppe bridging Ru-Ru bonds) can all be isolated in good yields. A full X-ray crystallographic analysis of Ru3(CO)10(η-dppe) shows that it crystallizes in the triclinic system, space group P, a 10.615(2), b 11.769(6), c 16.584(4) A, α 75.68(2), β 84.59(2), γ 69.64(2)°. The structure was refined to R = 0.030, Rw = 0.034 using 3558 data with I ⩾ 2.5 σI. The dppe ligand bridges a Ru-Ru bond (2.856(1) A), occupying equatorial sites on adjacent Ru atoms. Other distances: non-bridged RuRu bonds are 2.855(1), 2.847(1); RuP, 2.330(2) A.

Cyclopentadienyl-ruthenium and -osmium chemistry. Cleavage of tetracyanoethylene under mild conditions: X-ray crystal structures of [Ru{η3-C(CN)2CPhCC(CN)2}(PPh3)(η-C5H5)] and [Ru{C[C(CN)2]CPhC(CN)2}-(CNBut)(PPh3)(η-C5H5)]

The reaction between [RU(C2Ph)(PPh3)2(η-C5H5)] and C2(CN)4 affords [Ru{η3-C(CN)2 CPhCC(CN)2}-(PPh3)(η-C5H5)](2), which forms [Ru{C[C(CN)2]- CPhC(CN)2}(L)(PPh3)(η-C5H5)](5) with L = CO or CNBut; the structures of (2) and (5; L = CNBut) have been determined by X-Ray crystallography.

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 RuRu 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(CCPh)(dppe)(η-C5H5), the vinylidene [Ru(CCMePh)(PPh3)2(η-C5H5)]I and the carbene [Ru{C(OMe)Et}(PPh3)2(η-C5H5)][PF6], have enabled comparison of the RuC(α) bonds in these and a number of related complexes. Cationic complexes have RuC 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 RuC bond which can be ascribed to back-bonding from the metal to the unsaturated carbon-bonded ligand. Ru(CCPh)(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(CCMePh)(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.

Cluster chemistry. LI: Reactions of some substituted ruthenium and osmium cluster carbonyls with dihydrogen. X-ray crystal structures of Ru3(μ-H)2(μ3-PPh)(CO)8(PMePh2), Ru4(μ-H)4(μ-dppm)(CO)10, Ru4(μ-H)3(μ3-PPhCH2PPh2(CO)10 and Os3(μ-H)2(μ-dppm)(CO)8

Summary The reactions of dihydrogen (80°C, 20 bar, 2 h) with a series of tertiary phosphine and phosphite complexes Ru 3 (CO) 12- n (L) n (L) = PMe 3 , PPh 3 , PPh (OMe) 2 or P(OMe) 3 ; n = 1–3), and with complexes containing dppm, dppe, dpam and PPh 2 (C 6 H 4 CH=CH 2 -2) have been studied. Complexes containing monodentate ligands gave tetranuclear complexes Ru 4 (μ-H) 4 (CO) 12- n (L) n ( n = 0–3, but not 4), whereas complexes with bidentate ligands showed varying behaviour. Thus Ru 3 (μ-dppm)(CO) 10 gave Ru 3 (μ-H) 2 (μ 3 -PPhCH 2 PPh 2 )(CO) 9 , further hydrogenation of which afforded Ru 3 (μ-H) 2 (μ 3 -PPh)(CO) 8 (PMePh 2 ). Ru 3 (μ-dppe)(CO) 10 gave a mixture of Ru 3 (μ-H)(μ 3 -PPhCH 2 CH 2 PPh 2 )(CO) 9 and Ru 4 (μ-H) 4 (μ-dppe)(CO) 10 as the major products, and Ru 3 (μ-η 2 , P -CH 2 =CHC 6 H 4 PPh 2 )(CO) 10 gave a mixture of Ru 4 (μ-H) 4 (CO) 12 - n PPh 2 (C 6 H 4 Et-2) n ( n = 0 and 1). Pyrolysis of Ru 4 (μ-H) 4 (μ-dppm)(CO) 10 afforded Ru 4 (μ-H) 3 (μ 3 -PPhCH 2 PPh 2 )(μ-CO) 2 (CO) 8 . The molecular structures of Ru 3 (μ-H) 2 (μ 3 -PPh)(CO) 8 (PMePh 2 ), Ru 4 (μ-H) 4 )(μ-dppm)(CO) 10 and Ru 4 (μ-H) 3 (μ 3 -PPhCH 2 PPh 2 )(μ-CO) 2 (CO) 8 have been determined: 2286, 4930 and 6393 data ( I ≽ 2.5σ( I )) were refined to R and R w values of 0.032 and 0.037, 0.026 and 0.035, and 0.043 and 0.053, respectively. Hydrogenation of Os 3 (μ-dppm)(CO) 10 gave Os 3 (μ-H) 2 (μ-dppm)(CO) 8 , whose structure was also determined: 3367 data with I ≽ 2.5 σ( I ) were refined to R w 0.052.

The crystal structure of bis[N-(2-aminoethyl)salicylaldiminato] iron (III) chloride monohydrate, a low spin oron(III) complex stabilized by lattice water ☆

Abstract The crytal structure and molecular configuration of bis[N-(2-aminoethyl)salicylaldiminato] iron(III) chloride monohydrate, Fe(III)(Saen)2Cl·H2O, has been determined by X-ray diffraction techniques. The crystals are orthorhombic with space group Pbca and cell dimension a = 32.694(22), b = 10.085(7) and c = 12.274(8)A. The structure was solved by the heavy atom technique and refined by the full-matrix least-squares method with 1587 reflections to an R factor of 0.114 (on F). The iron atom is octahedrally coordinated by the two tridentate ligands in the meridional configuration. Strong hydrogen bonding occurs between the ammine hydrogens, water molecule and chloride ion, accounting for the stabilization of the low spin state in the hydrated solid over the high spin state found when dehydrated.

Cyclopentadienyl-ruthenium and -osmium chemistry: XXXII. Some complexes containing tertiary phosphites: X-ray structures of RuCl{P(OMe)3}2(η-C5H5) and of two isomers of Ru{C[C(CN)2]CPhC(CN)2}{P(OMe)3}2(η-C5H5)

Abstract Exchange of tertiary phosphites for PPh3 in RuCl(PPh3)2(η-C5H5) afforded RuCl{P(OR)3}2(η-C5H5) (R3  Me3, (CH2CF3)3, (CH2)3CEt). Conventional reactions of the P(OMe3) complex afforded RuX{P(OMe)3}2(η-C5H5 (X = H, C(CO2Me)CH(CO2Me), SnCl3, C2Ph, CCPhC(CN) 2 C (CN)2, C{C(CN)2}-CPHC(CN)2 (red and yellow forms)) or [Ru(L){P(OMe)3}2(η-C5H5)]+] [L = NCMe, C  CHPh, C(OMe)CH2Ph, CCMePh, CCClPh). The phenylethynyl complex was converted to two copper-containing complexes by coordination of CuCl or Cu+ to the C triple bond. Crystals of RuCl{P(OMe)3}2(η-C5H5) are orthorhombic, space group Pna21 with unit cell dimensions a 9.606(3), b 14.167(4) and c 12.891(4) A and Z = 4; Ru{C[C(CN)2]CPhC(CN)2}{P(OMe)3}2(η-C5H5 exists as two isomers: yellow form, triclinic, space group PI, a 9.496(6), b 10.436(6), c 15.216(2) A, α 90.74(2), β 90.22(3), γ 111.47(4)° and Z = 2; red form, orthorhombic, space group Pbca, a 14.501(5), b 15.047(2), c 26.658(4) A and Z = 4. The structures were each refined by a full-matrix least-squares procedure to final R = 0.051, Rw = 0.050 for 1419 reflections with I > 2.5σ(I) for RuCl{P(OMe)3}2(η-C5H5; R = 0.037, Rw = 0.041 for 2930 reflections for the yellow isomer of Ru{C[C(CN)2]CPhC(CN)2}{P(OMe)3}2(η-C5H5); and R = 0.033, Rw = 0.035 for 1661 reflections for the red isomer.

Reactions of transition metal acetylides: VI. Some addition reactions of substituted styrenes with Ru(C2R)(L)2(η-C5H5) (R = Me OR Ph; L2 = (CO, PPh3), (PPh3)2 OR (dppe)). X-ray crystal structure of Ru{C[C(CN)2]CPhCH(C6H4NO2-4)}(dppe)(η-C5H5) · 0.5CH2Cl2

Abstract Further studies of the reactions between ruthenium σ-acetylide complexes and electrophilic olefins CHArC(CN)(X) (Ar = C 6 H 4 NO 2 -4, Ph; X = CN; Ar = C 6 H 4 NO 2 -4, X = CO 2 Et) have shown the formation of allylic, butadienyl, and in one case, cyclobutenyl complexes. The direction of addition is such that the =C(CN)(X) group becomes attached to the α-carbon of the acetylide. This is confirmed by the X-ray structure of Ru{C[C(CN) 2 ]CPhCH(C 6 H 4 NO 2 -4)}(dppe)(η-C 5 H 5 ) · 0.5CH 2 Cl 2 , cr with cell dimensions a 28.81(1), b 9.661(2), c 30.782(8) A, β 95.02 (3)°, and Z = 8. The structure was refined by a least-squares procedure with the use of 4291 statistically significant reflections [ I > 2.5σ( I )] to R 0.075 and R w 0.076.

Reactions of transition metal σ-acetylide complexes X. Cycloaddition of tetracyanoethene to manganese, iron and nickel complexes, and hydration of a related tungsten complex. X-Ray structures of Fe{C[C(CN)2]CPhC(CN)2}(CO)2(η- C5H5) and Ni{C[C(CN)2]CPhC(CN)2} (PPh3)(η-C5H5)

Tetracyanoethene adds to phenylethynyl-metal complexes of manganese, iron or nickel to give the butadienyl derivatives ML n {C[C(CN) 2 ]CPhC(CN) 2 } (ML n = Mn(CO) 3 (dppe), Fe(CO) 2 (η-C 5 H 5 ) or Ni(PPh 3 )(η-C 5 H 5 )). In non-polar solvents, intermediate manganese and iron cyclobutenyl complexes L n M{CCPhC(CN) 2 C(CN) 2 } can be isolated, but rapidly isomerise to the butadienyl complexes. Structural assignments of the isomers can be made on the basis of IR ν(CN), ν(CC) absorptions and FAB MS fragmentation pathways. Crystals of Fe{C[(CN) 2 ]CPhC(CN) 2 }(CO) 2 (η-C 5 H 5 ) are triclinic, space group P with unit cell dimensions a 9.378(2), b 13.874(3), c 7.935(4) A, α 92.92(3), β 101.57(2), γ 108.78(1)° and Z = 2. Crystals of Ni{C[C(CN) 2 ]CPhC(CN) 2 }(PPh 3 )(η-C 5 H 5 ) are monoclinic, space group P 2 1 /c, with unit cell parameters a 13.765(6), b 10.89(2), c 20.753(8) A, β 95.55(2)° and Z = 4. Both structures were refined by a full-matrix least-squares procedure to final R 0.038, R w 0.044 for 2825 reflections with I ≥ 2.5σ(I) (Fe) and R 0.048, R w 0.054 for 1702 reflections with I ≥ 2.5σ( I ) (Ni).

Macrobicyclic chromium(III) hexaamine complexes

Le compose cristallise dans le systeme monoclinique, groupe P2 1 /c avec Z=4. Coordination octaedrique autour du cation. Etude electrochimique et photochimique