Photolysis of triruthenium μ3-alkyne complexes capped by a μ3-oxo ligand

Reaction of [WI2(CO)3(NCMe)2] with two equivalents of 1-phenyl-1-propyne (MeC2Ph) in CH2Cl2, and in the absence of light, gave the bis(1-phenyl-1-propyne) complex [WI2(CO)(NCMe)(η2-MeC2Ph)2] (1) in 77% yield. Treatment of equimolar quantities of 1 and NCR (R = Et, i-Pr, t-Bu, Ph) in CH2Cl2 afforded the nitrile-exchanged products, [WI2(CO)(NCR)(η2-MeC2Ph)2] (2-5) (R = Et (2), i-Pr (3), t-Bu (4), Ph (5)). Complexes 1, 2, and 5 were structurally characterized by X-ray crystallography. All three structures have the same pseudo-octahedral geometry, with the equatorial sites being occupied by cis and parallel alkyne groups, which are trans to the cis-iodo groups. The trans carbon monoxide and acetonitrile ligands occupy the axial sites. In structures 1 and 2, the methyl and phenyl substituents of the 1-phenyl-1-propyne ligands are cis to each other, whereas for the bulkier NCPh complex (5), the methyl and phenyl groups are trans to one another. This is the first time that this arrangement has been observed in the solid state in bis(alkyne) complexes of this type.Key words: bis(1-phenyl-1-propyne), carbonyl, nitrile, diiodo, tungsten(II), crystal structures.

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The reactions of linear conjugated diynes with Dicarbonyl(η-cyclopentadienyl)- cobalt and -rhodium

Australian Journal of Chemistry ◽

10.1071/ch9750285 ◽

1975 ◽

Vol 28 (2) ◽

pp. 285 ◽

Cited By ~ 13

Author(s):

RS Dickson ◽

LJ Michel

Keyword(s):

Thermal Degradation ◽

Aromatic Compound ◽

Substituted Benzenes ◽

Polycyclic Aromatic Compound ◽

Organic Products ◽

Polycyclic Aromatic ◽

Alkyne Complexes ◽

Conjugated Diynes

The reactions of (η-C5H5)Co(CO)2 with the diynes hexa-2,4-diyne and 1,4- diphenylbutadiyne give three isomers of the cyclopentadienone complexes (C5H5)Co[(RC2C2R)2CO], R = Me or Ph, and two isomers of the tris-alkyne complexes (C5H5)2Co2(RC2C2R)3CO, R = Me or Ph. Organic products of formula (RC2C2R)3, R = Me or Ph, (MeC2C2Me)5, and (PhC2C2Ph)3CO have been isolated also. Two isomers of (RC2C2R), were separated and were identified as the 1,2,4-(R)3-3,5,6-(C2R)3- and the 1,3,5-(R)3-2,4,6-(C2R)3-benzenes. The compound (PhC2C2Ph)3CO is believed to be tris(phenylethynly)triphenylcycloheptatrienone, and (MeC2C2Me)5 is probably a polycyclic aromatic compound. Thermal degradation of the complexes (C5H5)2CO2(RC2C2R)3CO gives the substituted benzenes (RC2C2R)3. �� The reaction of (η-C5H5)Rh(CO)2 and hexa-2,4-diyne gives the cyclopentadienone complex(C5H5)Rh[(MeC2C2Me)2CO] and the cycloheptatrienone complex (C5H5)Rh[(MeC2C2Me)3CO].Two isomers of the substituted benzene (MeC2C2Me)3 were obtained also.

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Preparation and Structure of Tetraphenylarsonium Bis[1,2-Dicyanoethenedithiolato]oxotechnetate(V)

Australian Journal of Chemistry ◽

10.1071/ch9880151 ◽

1988 ◽

Vol 41 (1) ◽

pp. 151 ◽

Cited By ~ 12

Author(s):

SF Colmanet ◽

MF Mackay

Keyword(s):

Bond Distance ◽

Apical Position ◽

Space Group ◽

Ethanol Yields ◽

Oxo Ligand

The reaction of sodium 1,2-dicyanoethenedithiolate with [AsPh4][TcOCl4] in ethanol yields crystals of [AsPh4][ TcO ( mnt )2] (1). Crystals of (1) are monoclinic and belong to the space group P21/c with a 12.636(1), b 13.749(1), c 18.484(1)Ǻ, β 93.49(1)� with Z 4. Refinement on 3669 data measured with Cu Kα radiation converged at R 0.063. The structure consists of [ TcO ( mnt )2]- anions and [AsPh4]+ cations. The technetium(V) atom is five-coordinate with the four sulfur atoms in the basal positions and the oxo ligand in the apical position, to give a distorted square-pyramidal environment about the technetium. The Tc =O bond distance is 1.655(6)Ǻ.

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An unusual ditantalum (Ta:Ta) compound with a bridging oxo ligand

Inorganic Chemistry ◽

10.1021/ic00148a005 ◽

1983 ◽

Vol 22 (6) ◽

pp. 868-870 ◽

Cited By ~ 8

Author(s):

F. Albert Cotton ◽

Wieslaw J. Roth

Keyword(s):

Oxo Ligand

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Zur Umsetzung von ReO2I(PPh3)2 mit PhNCO. Synthese und Kristallstrukturen von ReO2I(PPh3)2 · CHCl3, [ORe(OCONPh)I(PPh3)]3, Re(NPh)(NH2Ph)I2(PPh3)(OCONHPh) und Re(NPh)(NH2Ph)I2(PPh3) ( OReO3) / On the Reaction of ReO2I(PPh3)2 with PhNCO. Synthesis and Crystal Structures of ReO2I(PPh3)2 · CHCl3, [ORe(OCONPh)I(PPh3)]3, Re(NPh)(NH2Ph)I2(PPh3)(OCONHPh) and Re(NPh)(NH2Ph)I2(PPh3) ( OReO3)

Zeitschrift für Naturforschung B ◽

10.1515/znb-1991-0218 ◽

1991 ◽

Vol 46 (2) ◽

pp. 235-244 ◽

Cited By ~ 11

Author(s):

S. Schmid ◽

J. Strähle

Keyword(s):

Hydrolysis Product ◽

Phosphine Ligands ◽

Partial Hydrolysis ◽

Monoclinic Space Group ◽

Linear Arrangement ◽

Triclinic Space Group ◽

Metal Centers ◽

Space Group ◽

Trimeric Complex ◽

Oxo Ligand

PhNCO reacts with oxo ligands at metal centers to form phenyl nitrene complexes. As an intermediate of this reaction we obtained with ReO2I(PPh3)2 (1) the trimeric complex [ORe(OCONPh)I(PPh3)]3 (2) in which the PhNCO moiety was added to an oxo ligand to form an N -phenyl carbamato group. This group acts as a bridging ligand chelating one Re atom via its N and one O atom and coordinating an other Re atom by its second O atom . 2 crystallizes as 2 · 2 CHCl3 in the triclinic space group P1̄ with a = 1423.1(5), b = 2443.3(7), c = 1403.8(6) pm , α = 92.31(3), β = 94.76(3), γ = 81.48(3)°, and Z = 2. From the mother liquor of 2 after a few days Re(NPh)(NH2Ph)I2(PPh3)(OCONHPh) (3) is formed as a partial hydrolysis product. 3 is monoclinic with the space group P21/n and a = 1163.0(4), b = 2527.0(3), c = 1243.9(5) pm, β = 98.04°, Z = 4. The Re atom exhibits an octahedral coordination w ith the two I atom s in a ?ra«s-arrangem ent and the phenyl nitrene ligand trans to the m onodentate PhN HCO2 group. The coordination is completed by a phosphine and an aniline ligand. Reaction of 2 with excess PPh3 yields 1. It crystallizes from CHCl3 as 1 · CHCl3 in the monoclinic space group P21/n with a = 975.9(3), b = 2731(1), c = 1417.3(6) pm , β = 93.35° and Z = 4. In 1 the Re atom is pentacoordinated in form of a trigonal bipyram id with the two phosphine ligands in axial positions. A solution of 2 in THF forms Re(NPh)(NH2Ph)I2(PPh3) (OReO3) (4) upon exposure to air at room temperature. 4 is obtained as orthorhombic crystals with the space group Pca21 and a = 1727(1), b = 1064.2(4), c = 1765.7(9) pm , Z = 4, and is an analogue of 3 from which it can be derived by substituting the carbamato ligand by a perrhenat ion. In 3 and 4 the phenyl nitrene ligand is bound by a Re = N triple bond of 172 pm in a linear arrangement Re = N - Ph .

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