Terminal Carbonyl Ligands Research Articles

μ-Bis(diphenylarsanyl)methane-1:2κ2As:As′]nonacarbonyl-1κ3C,2κ3C,3κ3C-(triisopropyl phosphite-3κP)-triangulo-triruthenium(0)

The asymmetric unit of the title triangulo-triruthenium compound, Ru3(CO)9(μ-Ph2AsCH2AsPh2)(P[OCH(CH3)2]3) or [Ru3(C25H22As2)(C9H21O3P)(CO)9], contains two mol­ecules of the triangulo-triruthenium complex. The bis­(diphenyl­arsanyl)methane ligand bridges an Ru—Ru bond and the monodentate phosphite ligand binds to the third Ru atom. Both the arsine and phosphite ligands are equatorial with respect to the Ru3 triangle. Additionally, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The dihedral angles between the pairs of benzene rings bound to individual As atoms are 85.67 (8) and 75.91 (8) in the first independent mol­ecule and 74.64 (8) and 70.76 (9) in the second. In the crystal, mol­ecules are linked into a three-dimensional framework by inter­molecular C—H⋯O hydrogen bonds.

μ-Bis(diphenylarsanyl)methane-1:2κ2As:As']nonacarbonyl-1κ3C,2κ3C,3κ3C-[(4-methylsulfanylphenyl)diphenylphosphane-3κP]-triangulo-triruthenium(0)

In the title triangulo-triruthenium compound, [Ru3(C25H22As2)(C19H17PS)(CO)9], the bis­(diphenyl­arsanyl)methane ligand bridges an Ru—Ru bond and the monodentate phosphane ligand bonds to the third Ru atom. Both arsine and phosphane ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three phosphane-substituted benzene rings make dihedral angles of 57.91 (19), 84.31 (15) and 59.37 (18)° with each other. The dihedral angles between the two benzene rings are 60.9 (2) and 85.40 (18)° for the two diphenyl­arsanyl groups. In the crystal, mol­ecules are linked into a three-dimensional framework by inter­molecular C—H⋯O hydrogen bonds. Weak inter­molecular C—H⋯π inter­actions stabilize the crystal structure.

μ-Bis(di-o-tolylphosphanyl)methane-1:2κ2P:P′]decacarbonyl-1κ3C,2κ3C,3κ4C-triangulo-triruthenium(0)–methanol (8/1)

The asymmetric unit of the title compound, [Ru3(C29H30P2)(CO)10].1/8CH3OH, contains two triangulo-triruthenium mol­ecules with similar configurations and a methanol solvent mol­ecule (fractional site occupancy for the latter = 0.25). The bis­(di-o-tolyl­phosphan­yl)methane ligand bridges an Ru—Ru bond and its P atoms are equatorial with respect to the Ru3 triangle. The phosphine-substituted Ru atoms each bear one equatorial and two axial terminal carbonyl ligands whereas the unsubstituted Ru atom carries two equatorial and two axial terminal carbonyl ligands. The dihedral angles between the two benzene rings attached to each P atom are 76.26 (13) and 74.76 (15)° for the first mol­ecule and 77.21 (13) and 75.68 (14)° for the second. In the crystal, mol­ecules are linked into [001] chains via inter­molecular C—H⋯O hydrogen bonds. Weak inter­molecular C—H⋯π inter­actions also occur.

μ-Bis(diphenylphosphanyl)ethane-1:2κ2P:P′]nonacarbonyl-1κ3C,2κ3C,3κ3C-(triphenylstibine-3κSb)-triangulo-triruthenium(0)

The asymmetric unit of the title triangulo-triruthenium compound, [Ru3(C26H24P2)(C18H15Sb)(CO)9], consists of two crystallographically independent mol­ecules, A and B. The bis­(diphenyl­phosphan­yl)ethane ligand bridges an Ru—Ru bond and the monodentate stibine ligand bonds to the third Ru atom. Both the stibine and phosphine ligands are equatorial with respect to the Ru3 triangle. Additionally, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three stibine-substituted benzene rings make dihedral angles of 38.7 (3), 71.5 (3) and 70.0 (3)° with each other in mol­ecule A whereas these angles are 83.9 (3), 88.2 (3) and 56.8 (3)° in mol­ecule B. Similarly, the dihedral angles between the two benzene rings are 80.7 (3) and 87.6 (3)° for the two diphenyl­phosphanyl groups in mol­ecule A and 84.0 (3) and 72.6 (4)° in mol­ecule B. In the crystal, mol­ecules are linked into tetra­mers via inter­molecular C—H⋯O hydrogen bonds. Weak inter­molecular C—H⋯π inter­actions further stabilize the crystal structure.

μ-Bis(diphenylphosphanyl)ethane-1:2κ2P:P′]nonacarbonyl-1κ3C,2κ3C,3κ3C-[tris(4-(methoxyphenyl)arsane-3κAs]-triangulo-triruthenium(0) chloroform monosolvate

The asymmetric unit of the title triangulo-triruthenium compound, [Ru3(C21H21AsO3)(C26H24P2)(CO)9]·CHCl3, consists of one mol­ecule of the triangulo-triruthenium complex and one chloro­form solvent mol­ecule. The bis(diphenyl­phosphan­yl)ethane ligand bridges an Ru—Ru bond and the monodentate arsane ligand bonds to the third Ru atom. Both the arsane and phosphine ligands are equatorial with respect to the Ru3 triangle. Additionally, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three arsane-substituted benzene rings make dihedral angles of 52.72 (19), 63.03 (19) and 88.19 (19)° with each other. The dihedral angles between the two benzene rings are 85.8 (2) and 89.2 (2)° for the two diphenyl­phosphanyl groups. In the crystal, mol­ecules are linked together into a three-dimensional network via inter­molecular C—H⋯O hydrogen bonds. Weak inter­molecular C—H⋯π inter­actions further stabilize the crystal structure.

Bis{[μ-bis(diphenylphosphanyl)methane-1:2κ2P:P′]nonacarbonyl-1κ3C,2κ3C,3κ3C-[(4-methylsulfanylphenyl)diphenylphosphane-3κP]-triangulo-triruthenium(0)} dichloromethane monosolvate

The asymmetric unit of the title triangulo-triruthenium compound, 2[Ru3(C25H22P2)(C19H17PS)(CO)9]·CH2Cl2, contains one triangulo-triruthenium complex mol­ecule and one half-mol­ecule of the dichloro­methane solvent. The dichloro­methane solvent mol­ecule lies across a crystallographic inversion center leading to the mol­ecule being disordered over two positions of equal occupancy. The bis­(diphenyl­phosphan­yl)methane ligand bridges an Ru—Ru bond and the monodentate phosphane ligand bonds to the third Ru atom. All phosphane ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three phosphane-substituted benzene rings make dihedral angles of 87.18 (11), 59.59 (10) and 89.28 (11)° with each other. The dihedral angles between the two benzene rings are 78.48 (11) and 87.58 (11)° for the two diphenyl­phosphanyl groups. In the crystal, the mol­ecules are stacked along the a axis. Weak inter­molecular C—H⋯π inter­actions stabilize the crystal structure.

μ-Bis(di-o-tolylphosphanyl)methane-1:2κ2P:P′]nonacarbonyl-1κ3C,2κ3C,3κ3C-[diphenyl(phenylsulfanylmethyl)phosphane-3κP]-triangulo-triruthenium(0) dichloromethane 0.25-solvate

In the title compound, [Ru3(C29H30P2)(C19H17PS)(CO)9]·0.25CH2Cl2, the atoms of the dichloro­methane solvent mol­ecule have a fractional site occupancy of 0.25; the dichloro­methane mol­ecule is disordered about an inversion centre. The bis­(di-o-tolyl­phosphan­yl)methane ligand bridges an Ru—Ru bond and the monodentate phosphane ligand bonds to the third Ru atom; its S-bonded phenyl ring is disordered over two orientations in a 0.53 (4):0.47 (4) ratio. All the P atoms are equatorial with respect to the Ru3 triangle: each Ru atom also bears one equatorial and two axial terminal carbonyl ligands. The dihedral angles between the two benzene rings attached to each P atom of the diphenyl­phosphanyl ligand are 68.4 (2) and 71.5 (2)°. In the crystal, mol­ecules are linked into [001] chains via inter­molecular C—H⋯O hydrogen bonds. Weak inter­molecular C—H⋯π inter­actions also occur.

μ-Bis(diphenylphosphanyl)methane-1:2κ2P:P′]nonacarbonyl-1κ3C,2κ3C,3κ3C-[tris(biphenyl-4-yl)arsane-3κAs]-triangulo-triruthenium(0)

In the title triangulo-triruthenium compound, [Ru3(C36H27As)(C25H22P2)(CO)9], the bis­(diphenyl­phosphan­yl)methane ligand bridges an Ru—Ru bond and the monodentate arsine ligand bonds to the third Ru atom. Both the arsine and phosphine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. In each biphenyl unit, the phenyl rings are twisted from each other, making dihedral angles of 51.22 (18), 42.94 (16) and 26.95 (16)°. The arsine-substituted phenyl rings make dihedral angles of 61.22 (15), 87.17 (15) and 83.32 (15)° with each other. The dihedral angles between the two benzene rings are 85.52 (18) and 81.77 (15)° for the two diphenyl­phosphanyl groups, respectively. In the crystal, mol­ecules are linked into dimers by inter­molecular C—H⋯O hydrogen bonds. Weak inter­molecular C—H⋯π and π–π [centroid–centroid distance = 3.6981 (18) Å] inter­actions stabilize the crystal structure.

μ-Bis(diphenylarsanyl)methane-1:2κ2As:As']nonacarbonyl-1κ3C,2κ3C,3κ3C-[tris(biphenyl-4-yl)arsane-3κAs]-triangulo-triruthenium(0)

In the title triangulo-triruthenium compound, [Ru3(C25H22As2)(C36H27As)(CO)9], the bis­(diphenyl­arsan­yl)methane ligand bridges an Ru—Ru bond and the monodentate arsine ligand bonds to the third Ru atom. Both arsine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The phenyl rings of biphenyl are twisted from each other by dihedral angles of 50.5 (2), 44.5 (2) and 27.8 (2)°. The arsine-substituted phenyl rings make dihedral angles of 61.56 (18), 89.36 (18) and 83.27 (18)° with each other. The dihedral angles between the two benzene rings are 87.5 (2) and 81.95 (19)° for the two diphenyl­arsanyl groups. In the crystal, mol­ecules are linked into dimers by inter­molecular C—H⋯O hydrogen bonds. Weak inter­molecular C—H⋯π and π–π [centroid–centroid distance = 3.601 (3) Å] inter­actions stabilize the crystal structure.

Undecacarbonyl-1κ3C,2κ4C,3κ4C-[tris(2-chloroethyl) phosphite-1κP]-triangulo-triruthenium(0)

In the title triangulo-triruthenium compound, [Ru3(C6H12Cl3O3P)(CO)11], one equatorial carbonyl ligand is substituted by a monodentate phosphite ligand, leaving one equatorial and two axial carbonyl ligands on one Ru atom. The remaining two Ru atoms each carry two equatorial and two axial terminal carbonyl ligands. In the crystal structure, the mol­ecules are linked into a one-dimensional column along [100] by inter­molecular C—H⋯O hydrogen bonds.

Bis([μ-bis(diphenylarsino)methane-1:2κ2As:As']nonacarbonyl-1κ3C,2κ3C,3κ3C-{tris[4-(methylsulfanyl)phenyl]arsine-3κAs}-triangulo-triruthenium(0)) dichloromethane monosolvate

The asymmetric unit of the title triangulo-triruthenium compound, 2[Ru3(C25H22As2)(C21H21AsS3)(CO)9]·CH2Cl2, consists of one triangulo-triruthenium complex mol­ecule and one half of a dichloro­methane mol­ecule which lies across a crystallographic inversion center, leading to the disorder of this mol­ecule over two positions of equal occupancy. The bis­(diphenyl­arsino)methane ligand bridges an Ru—Ru bond and the monodentate arsine ligand bonds to the third Ru atom. All arsine ligands are equatorial with respect to the Ru3 triangle. Each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three methyl­sulfanyl-substituted benzene rings make dihedral angles of 70.02 (8), 82.85 (9) and 89.49 (8)° with each other. The dihedral angles between the two phenyl rings are 78.25 (9) and 86.59 (9)° for the two diphenyl­arsino groups. In the crystal, weak inter­molecular C—H⋯π inter­actions are observed.

Bis([μ-bis(diphenylphosphino)methane-1:2κ2P:P′]nonacarbonyl-1κ3C,2κ3C,3κ3C-{tris[4-(methylsulfanyl)phenyl]arsine-3κAs}-triangulo-triruthenium(0)) dichloromethane monosolvate

The asymmetric unit of the title triangulo-triruthenium compound, 2[Ru3(C21H21AsS3)(C25H22P2)(CO)9]·CH2Cl2, consists of one triangulo-triruthenium complex mol­ecule and one half of a dichloro­methane mol­ecule which lies across a crystallographic inversion center, leading to the disorder of this mol­ecule over two positions of equal occupancy. The bis­(diphenyl­phosphino)methane ligand bridges an Ru—Ru bond and the monodentate arsine ligand bonds to the third Ru atom. Both the arsine and phosphine ligands are equatorial with respect to the Ru3 triangle. Each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three arsine-substituted benzene rings make dihedral angles of 82.69 (9), 70.43 (9) and 89.45 (9)° with each other. The dihedral angles between the two benzene rings are 85.14 (11) and 77.61 (10)° for the two diphenyl­phosphino groups. In the crystal packing, mol­ecules are linked together into dimers via inter­molecular C—H⋯O hydrogen bonds and these dimers are stacked along the a axis. Weak inter­molecular C—H⋯π inter­actions are also present.

Nonacarbonyl-1κ3C,2κ3C,3κ3C-μ-bis(diphenylarsino)methane-1:2κ2As:As'-[tris(2-chloroethyl) phosphite-3κP]-triangulo-triruthenium(0)

In the title triangulo-triruthenium(0) compound, [Ru3(C25H22As2)(C6H12Cl3O3P)(CO)9], the bis­(diphenyl­arsino)methane ligand bridges an Ru—Ru bond and the monodentate phosphine ligand bonds to the third Ru atom. Both the arsine and phosphine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. In the crystal packing, the mol­ecules are linked by inter­molecular C—H⋯O hydrogen bonds into a three-dimensional framework. Weak inter­molecular C—H⋯π inter­actions further stabilize the crystal structure.

Undecacarbonyl-1κ3C,2κ4C,3κ4C-[tris(3-chlorophenyl)phosphine-1κP]-triangulo-triruthenium(0)

In the title triangulo-triruthenium compound, [Ru3(C18H12Cl3P)(CO)11], one equatorial carbonyl group has been substituted by the monodentate phosphine ligand, leaving one equatorial and two axial carbonyl substituents on the Ru atom. The remaining two Ru atoms each carry two equatorial and two axial terminal carbonyl ligands. The three benzene rings make dihedral angles of 87.83 (17), 69.91 (17) and 68.26 (17)° with each other. In the crystal structure, mol­ecules are linked into dimers by inter­molecular C—H⋯O hydrogen bonds. The mol­ecular structure is stabilized by an intra­molecular C—H⋯O hydrogen bond.

Decacarbonyl-1κ3C,2κ3C,3κ4C-bis[tris(3-chlorophenyl)phosphine]-1κP,2κP-triangulo-triruthenium(0) monohydrate

The asymmetric unit of the title triangulo-triruthenium compound, [Ru3(C18H12Cl3P)2(CO)10]·H2O, consists of one triangulo-triruthenium complex and one disordered water solvent molecule. Two of the 3-chloro­phenyl rings are disordered over two positions with refined site occupancies of 0.671 (3)/0.329 (3) and 0.628 (3)/0.372 (3). The water mol­ecule is disordered over two positions with refined site occupancies of 0.523 (7) and 0.477 (7). Two equatorial carbonyl groups have been substituted by the two monodentate phosphine ligands, leaving one equatorial and two axial carbonyl substituents on the two Ru atoms. The remaining Ru atom carries two equatorial and two axial terminal carbonyl ligands. In the crystal structure, mol­ecules are linked into columns along the a axis by inter­molecular C—H⋯Cl and C—H⋯O hydrogen bonds. The mol­ecular structure is stabilized by weak intra­molecular C—H⋯O hydrogen bonds.

μ-Bis(diphenylarsino)methane-1:2κ2As:As′]nonacarbonyl-1κ3C,2κ3C,3κ3C-[diphenyl(phenylsulfanylmethyl)phosphine-3κP]-triangulo-triruthenium(0) chloroform hemisolvate

The asymmetric unit of the title triangulo-triruthenium cluster, [Ru3(C25H22As2)(C19H17PS)(CO)9]·0.5CHCl3, contains of one mol­ecule of the triangulo-triruthenium complex and half a mol­ecule of the disordered (two positions of equal weight) chloro­form solvent. The bis­(diphenyl­arsino)methane ligand bridges an Ru—Ru bond and the monodentate phosphine ligand bonds to the third Ru atom. Both the arsine and phosphine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The benzene ring of phenyl­thio­methyl is disordered over two positions with refined site occupancies of 0.788 (11) and 0.212 (11). In the crystal packing, mol­ecules are linked into chains along b axis by inter­molecular C—H⋯O hydrogen bonds. Weak inter­molecular C—H⋯π inter­actions further stabilize the crystal structure.

μ-Bis(diphenylarsino)methane-1:2κ2As:As′][bis(4-methoxyphenyl)phenylphosphine-3κP]-nonacarbonyl-1κ3C,2κ3C,3κ3C-triangulo-triruthenium(0) dichloromethane 0.15-solvate

The asymmetric unit of the title triangulo-triruthenium compound, [Ru3(C25H22As2)(C20H19O2P)(CO)9]·0.15CH2Cl2, contains one mol­ecule of the triangulo-triruthenium complex and one partially occupied dichloro­methane solvent mol­ecule. The dichloro­methane solvent lies across a crystallographic inversion center leading to the mol­ecule being disordered over two positions of equal occupancy. The bis­(diphenyl­arsino)methane ligand bridges an Ru—Ru bond and the monodentate arsine ligand bonds to the third Ru atom. Both the arsine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three phospho­rus-bound benzene rings make dihedral angles of 72.7 (3), 80.9 (3) and 70.8 (2)° with each other. The dihedral angles between the two benzene rings are 79.9 (3) and 81.5 (2)° for the two diphenyl­arsino groups.

μ-Bis(diphenylarsino)methane-1:2κ2As:As']nonacarbonyl-1κ3C,2κ3C,3κ3C-(triphenyl phosphite-3κP)-triangulo-triruthenium(0)

The asymmetric unit of the title triangulo-triruthenium compound, [Ru3(C25H22As2)(C18H15O3P)(CO)9], contains two crystallographically independent but similar mol­ecules. The bis­(diphenyl­arsino)methane ligand bridges an Ru—Ru bond and the monodentate phosphite ligand bonds to the third Ru atom. Both the phosphite and arsine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. One of the triphenyl­phosphite benzene rings in one of the mol­ecules is disordered over two positions with refined site occupancies of 0.60 (3) and 0.40 (3). In the crystal packing, the mol­ecules are stacked along a axis. Intra­molecular C—H⋯O hydrogen bonds stabilize the mol­ecular structure and weak inter­molecular C—H⋯π inter­actions further stabilize the crystal structure. The crystal studied was a non-merohedral twin, the refined ratio of the twin components being 0.618 (1):0.382 (1).

μ-Bis(diphenylarsino)methane-1:2κ2As:As′]nonacarbonyl-1κ3C,2κ3C,3κ3C-[(pentafluorophenyl)diphenylphosphine-3κP]-triangulo-triruthenium(0) chloroform monosolvate

The asymmetric unit of the title triangulo-triruthenium compound, [Ru3(C25H22As2)(C18H10F5P)(CO)9]·CHCl3, contains one mol­ecule of the triangulo-triruthenium complex and one mol­ecule of the disordered chloro­form solvent. The bis­(diphenyl­arsino)methane ligand bridges an Ru—Ru bond and the monodentate phosphine ligand bonds to the third Ru atom. Both the arsine and phosphine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The phosphine-substituted benzene rings make dihedral angles of 68.43 (15), 65.14 (14) and 89.75 (14)° with each other. The dihedral angles between the two benzene rings are 80.70 (15) and 84.53 (16)° for the two diphenyl­arsino groups. In the crystal packing, the mol­ecules are linked into a plane parallel to bc by inter­molecular C—H⋯O and C—H⋯F hydrogen bonds. Weak inter­molecular C—H⋯π inter­actions further stabilize the crystal structure.

Bis{[μ-bis(diphenylarsino)methane-1:2κ2As:As′]nonacarbonyl-1κ3C,2κ3C,3κ3C-[tris(4-methoxyphenyl)arsine-3κAs]-triangulo-triruthenium(0)} dichloromethane solvate

The asymmetric unit of the title triangulo-triruthenium compound, 2[Ru3(C25H22As2)(C21H21AsO3)(CO)9]·CH2Cl2, contains one triangulo-triruthenium complex mol­ecule and one half of the dichloro­methane solvent. The dichloro­methane solvent lies across a crystallographic inversion center leading to the mol­ecule being disordered over two positions of equal occupancy. The bis­(diphenyl­arsino)methane ligand bridges an Ru—Ru bond and the monodentate arsine ligand bonds to the third Ru atom. Both the arsine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The trimethoxy­phenyl­arsino benzene rings make dihedral angles of 83.01 (8), 65.81 (8) and 76.20 (8)° with each other. The dihedral angles between the two benzene rings are 82.69 (9) and 78.83 (9)° for the two diphenyl­arsino groups. In the crystal packing, the mol­ecules are stacked along the a axis and weak inter­molecular C—H⋯π inter­actions stabilize the crystal structure.