Carbonyl halides of the Group VI transition metals. XX. Substituted dialkyldithiocarbamato complexes of molybdenum halocarbonyls and their oxidation

1970 ◽  
Vol 23 (6) ◽  
pp. 1111 ◽  
Author(s):  
R Colton ◽  
GG Rose
Keyword(s):  
Carbon Tetrachloride ◽  
Transition Metals ◽  
Mass Spectrometric ◽  
Acetone Solution ◽  
Group Vi ◽  
Derivatives Of

Complexes of the type Mo(CO)2RPh3(dtc)2 (R = P, As, Sb; dtc = dialkyldithiocarbamato) have been prepared by the interaction of sodium dialkyldithiocarbamates with, for example, dichlorobis(triphenylphosphine)trioarbonylmolybdenum(11). In solution the complexes are susceptible to oxidation, but the product obtained depends strongly upon the nature of the solvent used. In acetone solution oxidation yields complexes of the type No2O3(dtc)4; this reaction is very similar to that reported previously for the oxidation of the parent compounds Mo(CO)3(dtc)2 and Mo(CO)2(dtc)2. However, oxidation of Mo(CO)2RPh3(dtc)2 in carbon tetrachloride-benzene mixture gives molybdenum(VI) derivatives of empirical formulae MoO2(dtc)2. The properties of these compounds are different from those reported by Moore and Larson for other compounds of the same formula. Infrared and mass spectrometric studies have shown that our complexes are dimeric and it has been confirmed that those of Moore and Larson are monomeric.

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. 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.

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.

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. 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.

scholarly journals Carbonyl halides of the Group VI transition metals. II. Derivatives of molybdenum tetracarbonyl dibromide

1966 ◽  
Vol 19 (8) ◽  
pp. 1519 ◽  
Author(s):  
R Colton ◽  
IB Tomkins
Keyword(s):  
Transition Metals ◽  
Group Vi ◽  
Derivatives Of

Carbonyl halides of the Group VI transition metals. XVIII. Bis(diphenylphosphino)methane derivatives of iodocarbonyls of molybdenum

1970 ◽  
Vol 23 (2) ◽  
pp. 223 ◽  
Author(s):  
R Colton ◽  
JJ Howard
Keyword(s):  
Transition Metals ◽  
Isomeric Form ◽  
Group Vi ◽  
New Type ◽  
Derivatives Of

Bis(diphenylphosphino)methane, dpm, reacts with hexacarbonylmolybdenum to give Mo(CO)4 dpm and subsequently trans-Mo(CO)2(dpm)2. Oxidation of the tetracarbonyl derivative with iodine yielded Mo(CO)3(dpm)I2; reaction of this complex with further dpm gave Mo(CO)2(dpm)2I2. As with the corresponding tungsten system there are two isomers of Mo(CO)2(dpm)2I2 and three isomeric forms of Mo(CO)2(dpm)2I2 which can be obtained by this method of synthesis, all of which have been isolated and characterized individually. trans- Mo(CO)2(dpm)2 reacts with iodine to give a fourth isomeric form of the iododicarbonyl complex, trans- [Mo(CO)2(dpm)2]I2 which is a new type of halocarbonyl complex of molybdenum(11).

Carbonyl halides of the Group VI transition metals. XIV. Substitution derivatives of the trihalotetracarbonylmolybdenum(II) anions

1969 ◽  
Vol 22 (5) ◽  
pp. 905 ◽  
Author(s):  
JA Bowden ◽  
R Colton
Keyword(s):  
Transition Metals ◽  
Ammonium Salts ◽  
Group Vi ◽  
Complete Series ◽  
First Time ◽  
Derivatives Of

The complete series of substituted halocarbonyl anions [Mo(CO)3RPh3X3]- (where R is P, Sb, As; X is Cl, Br) have been characterized as their tetraethyl-ammonium salts. Each substituted anion has been prepared by two distinct methods and all of the compounds can exist as two isomers. Except for the α-isomer of [Mo(CO)3PPh3Br3]- these complexes are reported for the first time.

scholarly journals Carbonyl halides of the Group VI transition metals. X. Further dithiocarbamate derivatives of Molybdenum Halocarbonyls

1968 ◽  
Vol 21 (6) ◽  
pp. 1427 ◽  
Author(s):  
R Colton ◽  
GR Scollary
Keyword(s):  
Carbon Monoxide ◽  
Alkyl Group ◽  
Carbonyl Compounds ◽  
Mass Spectrometric ◽  
Group Vi ◽  
Molybdenum Carbonyl ◽  
The Stability ◽  
Derivatives Of ◽  
Dithiocarbamate Group ◽  
Dithiocarbamate Derivatives

The changes effected in the stability of molybdenum carbonyl compounds of the types Mo(CO), dtc, and Mo(CO), dtc, (dtc = dialkyldithiocarbamate) and in their carbon monoxide carrying ability, by varying the alkyl group in the dithiocarbamate group, have been investigated. The oxidation of the carbonyl dithiocarbamate complexes by oxygen to the known molybdenum(v) complexes of the type Mo2O3 dtc, is reported. Extensive infrared and mass spectrometric studies on the latter compounds have been carried out. Attempts to isolate the corresponding tungsten compounds have been unsuccessful.

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