ISSN:
0009-2940
Keywords:
Imido ligands
;
Oxo ligands
;
Pentamethylcyclopentadienyl ligand
;
Molybdenum complexes
;
Tungsten complexes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Organometallic Imido Complexes - Highervalent Derivatives of the d-Metal Acids, 3[4b]. - Synthesis and Reactions of Pentamethylcyclopentadienyl Imido Complexes of Molybdenum and Tungsten and an Efficient Strategy for the Synthesis of the Organometallates NBu4[Cp*MO3] (M = Mo, W)A convenient and new entry into the chemistry of highvalent pentamethylcyclopentadienyl halfsandwich complexes of molybdenum and tungsten is described. The reaction of Mo-(NtBu)2Cl2 or W(NtBu)2Cl2(py)2 with Cp*Li (Cp* = η5-C5Me5) provides a high-yield route to new complexes Cp*Mo-(NtBu)2Cl (1a) and Cp*W(NtBu)2Cl (1b) which are converted into a variety of diimido, monoimido, and oxo derivatives. Treatment of 1a,b with MeLi yields the highly volatile methyl derivatives Cp*Mo(NtBu)2Me (2a) and Cp*W(NtBu)2Me (2b), while protolysis of 1a,b with an excess of HCl gas leads to selective cleavage of only one imido function with formation of Cp*Mo(NtBu)Cl3 (3a) and Cp*W(NtBu)Cl3 (3b). In contrast, protolysis of 1a,b with aqueous HCl provides a high-yield route to the well-known organometallic oxides [Cp*MoO2]-(μ-O) (4a) and [Cp*WO2](μ-O) (4b). These two key compounds are easily converted into the organomolybdate and organotungstate salts NBu4[Cp*MoO3] (5a) and NBu4[Cp*WO3] (5b) by cleavage of the M-O-M bridge with NBu4[OH]. The X-ray structure of 3a is reported.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19921251109
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