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

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.


1972 ◽  
Vol 25 (7) ◽  
pp. 1393 ◽  
Author(s):  
JA Bowden ◽  
R Colton ◽  
CJ Commons

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.



1968 ◽  
Vol 21 (6) ◽  
pp. 1435 ◽  
Author(s):  
R Colton ◽  
GR Scollary

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.



1978 ◽  
Vol 9 (4) ◽  
Author(s):  
S. I. BEILIN ◽  
S. B. GOL'SHTEIN ◽  
B. A. DOLGOPLOSK ◽  
A. M. KRAPIVIN ◽  
E. I. TINYAKOVA ◽  
...  


1968 ◽  
Vol 21 (5) ◽  
pp. 1155 ◽  
Author(s):  
R Colton ◽  
CJ Rix

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.



1968 ◽  
Vol 21 (11) ◽  
pp. 2657 ◽  
Author(s):  
JA Bowden ◽  
R Colton

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.



1977 ◽  
Vol 142 (2) ◽  
pp. 145-148 ◽  
Author(s):  
S.I. Beilin ◽  
S.B. Golstein ◽  
B.A. Dolgoplosk ◽  
L.Sh. Guzman ◽  
E.I. Tinyakova


1971 ◽  
Vol 24 (12) ◽  
pp. 2461 ◽  
Author(s):  
R Colton ◽  
CJ Rix

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.



1968 ◽  
Vol 21 (1) ◽  
pp. 15 ◽  
Author(s):  
R Colton ◽  
GR Scollary ◽  
IB Tomkins

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.





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