Michael J. Liddell

Cluster chemistry: LVI. Stereochemistry of group 15 ligand-substituted derivatives of M3(CO)12 (M = Ru, Os) B. X-Ray structures of six complexes M3(CO)10(L)2 (M = Ru, L = PPh3, PPh(OMe)2, and P(OCH2CF3)3; M = Os, L = PPh3, PPh(OMe)2 and P(OMe)3)

Abstract X-Ray crystal structures of six complexes of the type M 3 (CO) 10 (L) 2 (M = Ru, L = PPh 3 , PPh(OMe) 2 , and P(OCH 2 CF 3 3 ; M = Os, L = PPh 3 , PPh(OMe) 2 and P(OMe) 3 ) have been determined. All contain a triangular M 3 core; the two phosphorus ligands occupy equatorial positions on adjacent metal atoms so that they are approximately trans to each other at the ends of the Mue5f8-M vector. In contrast to complexes M 3 (CO) 11 (L), there is no prounounced lengthening of the Mue5f8M bonds cis to the group 15 ligand. Other features, including twisting of the ML 4 groups to distort the D 3h symmetry towards D 3 , are similar to those found for monosubstituted complexes. Thermal reactions between Os 3 (CO) 12) and P(OMe) 3 , which afford Os 3 (CO) 12- n {P(OMe) 3 } n ( n = 1–4), are described. Crystal data: Ru 3 (CO) 10 (PPh 3 ) 2 : orthorhombic, P 2 1 2 1 2 1 , τa 34.636(15), b 17.007(10)(10), c 14.806(4) A, U 8721(7) A 3 , Z = 8, N 0 (number of ‘observed’ data with I > 3σ( I ) = 4773, R = 0.071, R ′ = 0.080; Os 3 (CO) 10 (PPh 3 2 : monoclinic, P 2 1 / n , a 17.104(6), b 34.507(11), c 14.832(6) A, β 92.28(3)°, U 8747(5) A 3 Z = 8, N 0 = 8011, R = 0.048, R ′ = 0.040; Ru 3 (CO) 10 {PPh(OMe) 2 } 2 : monoclinic, Pc, a 9.014(4), b 8.545(4), c 21.728(5) A, β 100.77(3)°, U 1644(1) A 3 , Z = 2, N 0 = 5269, R = 0.024, R ′ = 0.027; Os 3 (CO) 10 {PPh(OMe) 2 } 2 : monoclinic, Pc, a 9.007(5), b 8.565(7), c 21.716(12) A, β 100.87(5)°, U 1645(1) A 3 , Z = 2, N 0 = 5266, R = 0.041, R ′ = 0.043; Ru 3 (CO) 10 {P(OCH 2 CF 3 ) 3 } 2 : orthorhombic, P 2 1 2 1 2 1 , a 29.79(2), b 15.827(8), c 8.283(4) A, U 3906(3) A 3 , Z = 4, N 0 = 2652, R = 0.063, R ′ = 0.070; Os 3 (CO) 10 {P(OMe) 3 } 2 : triclinic, P 1 , a 24.955(10), b 9.439(4), c 8.944(4), A, a 84.02(3), β (3), γ 84.18(3)°, U 2083(1) A 3 , Z = 3, N 0 = 40.84, R = 0.057, R ′ = 0.068.

Cluster chemistry. LVII: Stereochemistry of group 15 ligand-substituted derivatives of M3(CO)12 (M=Ru, Os). C. X-ray structures of Ru3(CO)9(L)3 (L=PMe2(CH2Ph), PMe2Ph, AsMe2Ph, PPh(OMe)2, P(OEt)3, and P(OCH2CF3)3) and Os3(CO)9(PPh3)3

The molecular structures of Ru3(CO)9(L)3 (L = PMe2(CH2Ph), PMe2Ph, AsMe2Ph, PPh(OMe)2, P(OEt)3 and P(OCH2CF3)3) and Os3(CO)9(PPh3)3 have been determined by single-crystal X-ray diffraction methods. The tertiary phosphine, arsine or phosphite ligands occupy equatorial sites, one per metal atom, so arranged that each is as far from the other two as possible. The unit cell of the PPh(OMe)2 complex is unusual in containing four conformationally distinct molecules, two of which contain disordered Ru3 cores. Metalue5f8metal and metalue5f8ligand separations are similar to those found in Me3(CO)12 and mono- or disubstituted complexes, respectively. Considerable distortion towards D3 symmetry is found, with Mue5f8Mue5f8CO angles approaching those calculated for semi-bridging CO groups in the case of the P(OEt)3 complex. Crystal data: Ru3(CO)9(PMe2Ph)3, orthorhombic, P212121, a 21.343(2), b 14.752(4), c 12.170(2) A, U 3832(1) A3, Z = 4, N0 (number of ‘observed’ data with I > 3σ(I)) = 3601, R = 0.040, R′ = 0.048; Ru3(CO)9-(AsMe2Ph)3, triclinic, P1, a 19.113(4), b 15.375(4), c 13.756(3) A, α 89.36(2), β 85.97(2), γ 77.61(2) °, U 3939(2) A3, Z = 4, N0 = 8823, R = 0.046, R′ = 0.047; Ru3(CO)9{PMe2(CH2Ph)}3, trigonal, P3, a 12.766(10), c 15.583(9) A, U 2202(2) A3, Z = 2, N0 = 1966; R = 0.093, R′ = 0.117; Ru3(CO)9{PPh(OMe)2}3, triclinic, P1, a 23.23(1), b 20.87(1), c 20.73(1) A, α 98.21(4), β 111.07(3), γ 111.95(4) °, U 8237(7) A3, Z = 8, N0 = 16532, R = 0.041, R′ = 0.039; Ru3(CO)9{P(OEt)3}3, triclinic, P1, a 18.170(6), b 13.016(6), c 10.035(3) A, α 68.83(3), β 80.42(3), γ 78.10(4) °, U 2154(1) A3, Z = 2, N0 = 4318, R = 0.051, R′ = 0.061; Ru3(CO)9{P(OCH2CF3)3}3, triclinic, P1, a 21.036(2), b 13.146(1), c 9.376(2) A, α 82.68(1), β 88.40(1), γ 85.59(1) °, U 2564(1) A3, Z = 2, N0 = 3966, R = 0.066, R′ = 0.068; Os3(CO)9(PPh3)3, triclinic, P1, a 18.207(5), b 17.911(6), c 12.928(3) A, α 94.13(2), β 98.98(2), γ 110.56(2) °, U 3862(2) A3, Z = 2, N0 = 3216, R = 0.092, R′ = 0.084.

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[ue5fbC(CN) 2 ]CPhue5fbC(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{Cue5fbCPhC(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[ue5fb(CN) 2 ]CPhue5fbC(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[ue5fbC(CN) 2 ]CPhue5fbC(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).

Cluster chemistry LXIII. Further studies of the thermal behaviour of Ru3(CO)112(μ-dppa) (dppa = C2(PPh2)2). Crystal structures of Ru4(μ4-PPh)(μ4-PhC2PPh2)(μ-CO)2(CO)8·MeOH, Ru5(μ4-PPh) μ3-CCPh(PPh2)(CO)12, Ru5(μ3-H)(μ4-PPh)μ4-CCPh(C6H4) G80 (μ3-PPh)(CO)10 and Ru5(μ4-PPh) μ4-CCPh(C6H4)μ-PPh(OMe) (CO)11 · 2MeOH · H2O G80

Abstract Large scale (ca. 2 g) preparations of Ru 5 (μ 5 -C 2 PPh 2 )(μ-PPh 2 )(CO) 13 ( 2 ) by pyrolysis of Ru 3 (CO) 11 2 (μ-dppa) have also afforded the complexes Ru 4 (μ 4 -PPh)(μ 4 -PhC 2 PPh 2 )(μ-CO) 2 (CO) 8 ( 3 ), Ru 5 (μ 5 -C 2 PPh 2 )(μ-PPh 2 )(CO) 15 ( 4t ), Ru 4 (μ 4 -C 2 )(μ-PPh 2 ) 2 (CO) 12 ( 5 ), Ru 5 (μ 4 -PPh)μ 3 -CCPh(PPh 2 )(CO) 12 ( 6 ) and Ru 5 (μ-H)(μ 4 -PPh)μ 4 -CCPh(C 6 H 4 )(μ 3 -PPh)(CO) 10 ( 7 ). The new complexes 6 and 7 , identified crystallographically, are formed by heating 2 ; the evolved CO reacts with 2 to give 4t and 7 . Complex 6 contains a square pyramidal Ru 5 core, the square face being capped by PPh, and a triangular face by the phosphino-vinylidene ligand, which is formed by migration of Ph from P to C β of the C 2 PPh 2 ligand in 2 . Complex 7 contains a CPRu 5 pentagonal bipyramid, with PPh capping an Ru 3 face. Complex 7 reacts with MeOH to give Ru 5 (μ 4 -PPh)μ 4 -CCPh(C 6 H 4 )μ-PPh(OMe)(CO) 11 G80 ( 12 ), with the same core as 7 ; the μ 3 -PPh group has been converted to a μ-phosphido ligand. In 7 and 12 , the organic fragment is a metallated diphenylvinylidene. Some 31 P NMR data for these and related complexes are given and discussed. The crystal structure of 3 as its methanol solvate is also reported.

Cluster Chemistry: LIX. Stereochemistry of group 15 ligand-substituted derivatives of M3(CO)12 (M = Ru, Os). D. Synthesis and characterisation of some tetra-substituted ruthenium complexes: X-ray structures of Ru3(CO)8(L)4 (L = PMe2Ph and P(OR)3, R = Me, Et and Ph)☆

Abstract Several tetra-substituted derivatives of Ru 3 (CO) 12 have been synthesised, and the molecular structures of Ru 3 (CO) 8 (L) 4 (L = PMe 2 Ph and P(OR) 3 , R = Me, Et, Ph) have been determined by single-crystal X-ray diffraction methods. The non-carbonyl ligands occupy equatorial positions in the Ru 3 triangle, one on each of two metal atoms, and two on the third. Twisting of the ML 4 moieties about the Ruue5fbRu bonds is found, leading to the presence of one μ-CO ligand in the PMe 2 Ph and P(OEt) 3 complexes; the latter also has two semi-bridging CO ligands about the other two Ruue5f8Ru bonds. The PMe 2 Ph and P(OEt) 3 complexes exhibit 50 50 disorder of the Ru 3 core about a crystallographic inversion centre; the P(OMe) 3 complex has a similar 15 85 disorder in the Ru 3 core, and also in two of the OMe groups on one P(OMe) 3 ligand. A discussion of the major structural features of M 3 (CO) 12− n (L) n ( n = 1–4) is given. Crystal data: Ru 3 (CO) 8 (PMe 2 Ph) 4 , triclinic, P 1 , a 12.040(2), b 10.482(6), c 9.549(4) A, α 86.26(4), β 69.69(3), γ 78.72(3)°, U 1108.4(6) A 3 , Z = 1, N 0 (number of observed data with I > 3σ( I )) = 2056, R = 0.076, R ′ = 0.075; Ru 3 (CO) 8 {P(OMe) 3 } 4 , monoclinic, P 2 1 , a 9.821(2), b 17.384(6), c 10.912(3) A, β 94.88(2)°, U 1856(1) A 3 , Z = 2, N o = 2726, R = 0.041, R ′ = 0.046: Ru 3 (CO) 8 {P(OEt) 2 } 4 , monoclinic, C2 / c , a 18.987(6), b 12.465(4), c 22.244(7) A, β 102.03(3)°, U 5149(3) A 3 , Z = 4, N 0 ( I > 2σ( I ) = 1729, R = 0.066, R ′ = 0.048; Ru 3 (CO) 8 {P(OPh) 3 } 4 , monoclinic, P 2 1 / c , a 21.14(1), b 13.820(9), c 27.24(3) A, β 106.34(6)°, U 7637(7) A 3 , Z = 4, N 0 ( I > 2σ( I )) = 6107, R = 0.073, R ′ = 0.052.

Cyclopentadienyl-ruthenium and -osmium chemistry: XXXVI. Oligomerisation of phenylacetylide residues on ruthenium. Crystal structures of {Ru(PPh3)(η-C5H5)}2(μ-C8Ph4) and {Ru(PPh3)(η-C5H5)}2{μ-C10Ph4(C6H4)}

Abstract Reactions between RuCl(PPh3)2(η-C5H5) and AgC2Ph afforded a deep blue binuclear complex, shown by X-ray crystallography to contain a planar tricyclic diruthenadicyclobutadien[a, c]benzene system, formed by tetramerisation of phenylacetylide residues at the ruthenium centres. A deep purple complex, isolated in small yield from the same reaction, was similarly shown to contain a diruthenapentacyclic system, formed by an unprecedented oligomerisation of five phenylacetylide units. Related reactions have given [{Ru(C2Ph)(PPh32(η-C5H5)}2Ag][PF6] and the divinylidene [{Ru(PPh3)2(η-C5H5)}2(μ-C4Ph2)][PF6]2.

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.

Inclusion and aggregation properties of organogold complexes: crystal structures of C2Au[P(C6H4R-3)3]2·nC6H6 (R = H, n = 2; R = Me, n = 0 and 1)

The digold acetylides C2Au[P(C6H4R-3)32 (R = H or Me) from inclusion complexes in which two molecules (R = H) or one (R = Me) are present in cavities formed by the aryl groups; both complexes show unusual aggregation behaviour in the vapour phase, tetrameric ions being found in their FAB mass spectra.

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.

Fast-atom bombardment (FAB) mass spectra of coordination complexes: aggregation processes in the mass spectra of Group 11 alkynyl complexes

Abstract The FAB mass spectra of M(C2Ph)(PPh3) (m = Cu, Ag, Au) and C2{Au(PR3)}2 (R = Ph, m-tolyl) have been studied and the fragmentation routes determined by a combination of MIKES and B2/E techniques. A particular feature in the spectra of both types of complex is the presence of aggregate ions containing up to twelve metal atoms. For M(C2Ph)(PPh3), these ions have the compositions [ma(C2Ph)b(PPh3)+ (a ≥ b ≥ c; for Cu, a = 1-4; Ag, 1-3; Au, 1-4), although [Cu5(C2Ph)3(PPh 3)3]+ was detected in the B2/E scan. Fragmentation involves loss of PPh3, Ph or C2Ph groups. For C2{(Au(PR3)}2, loss of PR3 is the predominant fragmentation mode. In general, the ions are derived from several, rather than one, higher nuclearity ions. In both series, many ions can be considered to be formed by addition of [m(PR3)]+ cations to neutral oligometric Mn species; these ions are isolobal with protonated Mn ions.