| Publication Type |
Journal Article |
| Title |
Aminocarbyne and isocyanide complexes of rhenium. Crystal structures of trans-[ReCl(CNR)(Ph2PCH2CH2PPh2)(2)] (R = H or SiMe3) |
| Authors |
M. Fátima C. Guedes da Silva MANDA Lemos J.J.R. Fraústo da Silva Armando J.L. Pombeiro MA Pellinghelli A Tiripicchio |
| Groups |
|
| Journal |
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS |
| Year |
2000 |
| Month |
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|
| Volume |
|
| Number |
3 |
| Pages |
373-380 |
| Abstract |
Treatment of a thf solution of trans-[ReCl(N-2)(dppe)(2)] with an excess of NCSiMe3 in sunlight led to the formation of trans-[ReCl(CNSiMe3)(dppe)(2)] 1 in which the trimethylsilyl isocyanide ligand undergoes desilylation by acid or MeOH to give the aminocarbyne trans-[ReCl(CNH2)(dppe)(2)]A 2 (A=BF4 or Cl) upon treatment with an excess of HBF4 or HCl or the isocyanide trans-[ReCl(CNH)(dppe)(2)] 3 upon treatment with a stoichiometric amount of HCl or with MeOH. Complexes 2 convert into 3 by reaction with [NBu4]OH or NEt3 (a more convenient route for 3 than the above), and conversely are obtained from the reaction of 3 with HBF4 or HCl. Anodic controlled potential electrolysis of a solution of 2 (A=BF4) in 0.2 mol dm(-3) [NBu4][BF4]-NCMe, until the consumption of 2 F mol(-1), resulted in complete deprotonation of the aminocarbyne ligand to give the cyano-complex trans-[ReCl(CN)(dppe)(2)][BF4] 4 which, upon hydrogen abstraction from the electrolytic medium, converts into the isocyanide compound 3(+) isolated as trans-[ReCl(CNH)(dppe)(2)][BF4]. 2[NBu4][BF4]. The detailed syntheses and spectroscopic properties of all these complexes are reported, as well as the crystal structures of 1 and 3, and are discussed in terms of electronic and stereochemical properties of the ligands and binding metal centres. |
| DOI |
http://dx.doi.org/10.1039/a908174g |
| ISBN |
|
| Publisher |
ROYAL SOC CHEMISTRY |
| Book Title |
|
| ISSN |
0300-9246 |
| EISSN |
|
| Conference Name |
|
| Bibtex ID |
ISI:000084955900024 |
| Observations |
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