Carbonyl halides of the Group VI transition metals. XXVI. Nitrosyl halide complexes of molybdenum(II) and tungsten(II) with Bis(diphenyl-phosphino)methane and Bis(diphenylarsino)methane

1972 ◽  
Vol 25 (7) ◽  
pp. 1393 ◽  
Author(s):  
JA Bowden ◽  
R Colton ◽  
CJ Commons
Keyword(s):  
Nitric Oxide ◽  
Transition Metals ◽  
Direct Interaction ◽  
Group Vi ◽  
Halide Complexes ◽  
Derivatives Of ◽  
And Tungsten

The known polymeric molybdenum nitrosyl halides [Mo(NO)2X2 (X = Cl, Br) have been prepared by the action of nitric oxide on Mo(CO)4X2. Derivatives of these complexes with bis(diphenylarsino)methane (dam) and its phosphine analogue (dpm) were prepared by direct interaction. In addition, complexes containing dam were formed by the action of nitric oxide on M(CO)2(dam)2X2 (M = Mo, W; X = Cl,Br,I). All compounds isolated were of the form M(NO)2LX2 and M(NO)2L2X2 (L = dam or dpm). Differences between the nitrosyl halide derivatives and the corresponding carbonyl halide complexes are interpreted on the basis of a steric argument.

Carbonyl halides of the Group VI transition metals. VII. Nitrosyl halide derivatives of molybdenum and tungsten(II)

1968 ◽  
Vol 21 (5) ◽  
pp. 1149 ◽  
Author(s):  
MW Anker ◽  
R Colton ◽  
IB Tomkins
Keyword(s):  
Nitric Oxide ◽  
Transition Metals ◽  
New Method ◽  
Natural Explanation ◽  
Group Vi ◽  
New Feature ◽  
Derivatives Of ◽  
And Tungsten

The previously reported dihalodinitrosylbis(triphenylphosphine)molybdenum and tungsten(11) type complexes, M(NO)2L2X2 (M = Mo, W; L = PPh3, AsPh3, SbPh3; X = Cl, Br), have been prepared by a new method involving the action of nitric oxide on the corresponding tricarbonyl derivatives. The new feature of this method is that, unlike the previous methods, it is not stereospecific, and in some cases all three possible cis isomers are formed. The identification of the various isomers has given a natural explanation of the apparently anomalous order of π-bonding effects in these complexes previously reported by Cotton and Johnson.

Carbonyl halides of the Group VI transition metals. XI. Dithiocyanatocarbonyl derivatives of molybdenum and tungsten(II)

1968 ◽  
Vol 21 (6) ◽  
pp. 1435 ◽  
Author(s):  
R Colton ◽  
GR Scollary
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Ammonium Chloride ◽  
Pure State ◽  
Ammonium Thiocyanate ◽  
Donor Ligands ◽  
Group Vi ◽  
Derivatives Of ◽  
And Tungsten

Reaction of ammonium thiocyanate with dihalocarbonyls of molybdenum and tungsten(11) leads to the elimination of ammonium chloride and the formation of a dithiocyanatocarbonyl complex of the transition metal. Although the thiocyanatocarbonyls themselves have not been isolated in a pure state, a number of substituted derivatives with phosphorus donor ligands have been prepared and characterized. In general these complexes are less stable than the corresponding carbonyl halide derivatives.

Carbonyl halides of the Group VI transition metals. V. Carbon monoxide carriers and some sulphur and nitrogen derivatives of molybdenum halocarbonyls

1968 ◽  
Vol 21 (1) ◽  
pp. 15 ◽  
Author(s):  
R Colton ◽  
GR Scollary ◽  
IB Tomkins
Keyword(s):  
Carbon Monoxide ◽  
Transition Metals ◽  
Direct Interaction ◽  
Group Vi ◽  
Derivatives Of

The blue compounds MX2(CO)2(Ph3P)2 (M = Mo and W, X = Cl and Br) have been shown to absorb carbon monoxide very readily indeed to form the corresponding tricarbonyls, and as reported earlier, the tricarbonyls may be easily converted into the dicarbonyls. The dicarbonyl is therefore a carbon monoxide carrier. The compounds Mo(CO)3 dtc2 and Mo(CO)2 dtc2 (dtc = diethyldithiocarbamate) also represent a carbon monoxide carrying system, but in this case both compounds are rather unstable. The compounds MoX2(CO)2 btp2 (btp = N-n-butylthiopicolinamide; X = Cl, Br) have been prepared by direct interaction of the ligand and the appropriate halocarbonyl. Although these compounds are believed to be monomeric they do not absorb carbon monoxide.

Carbonyl halides of the Group VI transition metals. XIX. Iodocarbonyl complexes of molybdenum and tungsten with Bis(diphenylarsino)methane

1970 ◽  
Vol 23 (3) ◽  
pp. 441 ◽  
Author(s):  
R Colton ◽  
CJ Rix
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Carbon Monoxide ◽  
Magnetic Resonance ◽  
Transition Metals ◽  
Direct Interaction ◽  
Acetone Solution ◽  
Group Vi ◽  
First Time ◽  
And Tungsten ◽  
Nuclear Magnetic

Complexes of the general formulae M(CO)3(dam)I2, M(CO)3(dam)2I2, and M(CO)2(dam)2I2 have been prepared and characterized [M = Mo, W; dam = bis(diphenylarsino)methane]. All of the compounds are diamagnetic and non-electrolytes in acetone solution. The tungsten derivatives were prepared by direct interaction of dam with diiodotetracarbonyltungsten(11), but the molybdenum analogues were obtained by iodine oxidation of the zero-valent complex Mo(CO)4(dam)2 whose preparation is reported for the first time in this paper. The bis(dam)tricarbonyl complexes, M(C0)3(dam)2I2, are unstable in solution giving M(CO)2(dam)I2 and free dam in equilibrium with undissociated complex. The bis(dam)tricarbonyl complexes also readily lose carbon monoxide, especially in the case of molybdenum, to give M(CO)z(dam)2I2. These dicarbonyl complexes readily absorb carbon monoxide to re-form the tricarbonyl complexes to give a reversible carbon monoxide carrying system. Overall, these systems may be represented by the general equations : M(CO)3(dam)I2 + dam ↔ M(CO)3(dam)2I2 + CO These equilibria have been studied using both infrared and nuclear magnetic resonance techniques.

Carbonyl nitrosyl halide complexes of molybdenum and tungsten. II. Triarylphosphine and arsine complexes of tungsten

1973 ◽  
Vol 26 (7) ◽  
pp. 1487 ◽  
Author(s):  
R Colton ◽  
CJ Commons
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Nuclear Magnetic Resonance Spectra ◽  
Halide Complexes ◽  
Trans Complex ◽  
Derivatives Of ◽  
And Tungsten ◽  
Magnetic Resonance Spectra ◽  
Nuclear Magnetic

Triphenylphosphine and triphenylarsine derivatives of W(CO)4(NO)X (X = Cl, Br, I) have been prepared. These compounds have the form mer- W(CO)3(NO)LX, cis-W(CO)2(NO)L2X, and trans-W(CO)2(NO)(PPh3)2X. A trans complex with triphenylarsine could not be prepared. Further substitution with either ligand was not achieved. In addition, the tri(ortho-, meta-, and para-)tolylphosphine and arsine complexes of W(CO)4(NO)I have been isolated. Their nuclear magnetic resonance spectra indicate interaction between neighbouring ligands in some cases, and suggest that possible rotation about the metal-phosphorus and arsenic bonds may occur in these compounds.

Carbonyl halides of the Group VI transition metals. VIII. Paramagnetic and diamagnetic dicarbonyl derivatives of molybdenum(II)

1968 ◽  
Vol 21 (5) ◽  
pp. 1155 ◽  
Author(s):  
R Colton ◽  
CJ Rix
Keyword(s):  
Electron Spin Resonance ◽  
Transition Metals ◽  
General Formula ◽  
Electron Spin ◽  
Group Vi ◽  
Spin Resonance ◽  
Derivatives Of

Complexes of the general formula Mo(CO)2L2X2 (L = pyridine (py), 2,2'- dipyridyl (dipy), 1,l0-phenanthroline (phen); X = Cl, Br) have been isolated. The pyrldine derivatives are yellow monomeric compounds which are paramagnetic, but the complexes with dipy and phen contain diamagnetic seven-coordinate cations and are correctly formulated as [Mo(CO)2L2X]+X-. Conductance, infrared, magnetic, and electron spin resonance studies have been carried out.

Carbonyl halides of the Group VI transition metals. XII. Isolation of halocarbonyls and halocarbonyl anions of molybdenum and tungsten

1968 ◽  
Vol 21 (11) ◽  
pp. 2657 ◽  
Author(s):  
JA Bowden ◽  
R Colton
Keyword(s):  
Transition Metals ◽  
Group Vi ◽  
Tetraethylammonium Salts ◽  
And Tungsten

Dibromotetracarbonylmolybdenum, Mo(CO)4Br2, and the dihalotetracarbonyltungsten compounds, W(CO)4X2 (where X = Cl, Br), have been isolated and characterized. These highly reactive compounds are all diamagnetic. The trihalotetracarbonyl anions [M(CO)4X3]- (M = Mo, W) have been isolated as their tetraethylammonium salts from the parent halocarbonyls. These yellow diamagnetic compounds are the first tetracarbonyl derivatives to be prepared from the parent halocarbonyls.

Carbonyl halides of the Group VI transition metals. XVI. Reactions of Bis(diphenylphosphino)methane with Diiodotetracarbonyltungsten(II)

1969 ◽  
Vol 22 (12) ◽  
pp. 2535 ◽  
Author(s):  
R Colton ◽  
CJ Rix
Keyword(s):  
Carbon Monoxide ◽  
Transition Metals ◽  
Molecular Species ◽  
Direct Interaction ◽  
Ionic Species ◽  
Reaction Scheme ◽  
Simple System ◽  
Tricarbonyl Complex ◽  
Group Vi ◽  
Unusual Type

Compounds of the general formulae W(CO)3dpmI2 and W(CO)2(dpm)2I2 [dpm = bis(diphenylphosphino)methane] have been prepared by direct interaction of the ligand with diiodotetracarbonyltungsten(II). However, this apparently simple system is complicated by the existence of two isomers of the tricarbonyl complex and three isomeric forms of the dicarbonyl. The various isomers have been separated and characterized individually and the interconversions between all the complexes have been investigated. The overall reaction scheme contains a partial carbon monoxide carrying system and an example of an unusual type of isomerism: �������������������� W(CO)2(dpm)2I2 → [W(CO)2(dpm)2I]I that is, isomerism of a molecular species to an ionic species.

Substituted carbonyl derivatives of the Group VI transition metals. I. Complexes with Bis(diphenylarsino)methane

1971 ◽  
Vol 24 (12) ◽  
pp. 2461 ◽  
Author(s):  
R Colton ◽  
CJ Rix
Keyword(s):  
Transition Metals ◽  
X Ray Diffraction ◽  
Monodentate Ligand ◽  
Group Vi ◽  
X Ray ◽  
Carbonyl Derivatives ◽  
Physical Measurements ◽  
Novel Structure ◽  
Derivatives Of ◽  
Mode Of Coordination

The reactions of the potentially bidentate ditertiary arsine ligand bis-(diphenylarsino)methane, dam, with the hexacarbonyls of the Group VI transition metals have been investigated. N.m.r, spectroscopy has been used to determine the mode of coordination of the ligand. In the compounds M(CO)5(dam), M(CO)4(dam)2, and M(CO)3(dam)3 [M = Cr, Mo, W], dam is acting as a monodentate ligand, but in M(CO)4(dam) it is acting as a normal chelate coordinating to the metal through both arsenic atoms. In the cases of molybdenum and chromium, only, a further type of complex M(CO)2(dam) has been isolated. The results of N.M.R., infrared, and mass spectrometry, together with other physical measurements, can only be explained on the assumption that the ligand was coordinated to the metal by an arene π-linkage and by one arsenic atom. This novel structure has been confirmed by a single crystal X-ray diffraction study on the chromium compound.

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