Article: Synthetic and reaction chemistry of heteroatom stabilized boryl and cationic borylene complexes.
Dalton transactions (Cambridge, England : 2003)
2006 , Issue 2, Page(s) 399–410
Abstract: The synthesis, spectroscopic and structural characterization of the aryloxy and amino functionalized chloroboryl complexes (eta(5)-C(5)R(5))Fe(CO)(2)B(OMes)Cl (R = H, 2a ... R = Me, 3a) and (eta(5)-C(5)H(5))Fe(CO)(2)B(N(i)Pr(2))Cl (7a) are reported. ... ...
| Abstract | The synthesis, spectroscopic and structural characterization of the aryloxy and amino functionalized chloroboryl complexes (eta(5)-C(5)R(5))Fe(CO)(2)B(OMes)Cl (R = H, 2a R = Me, 3a) and (eta(5)-C(5)H(5))Fe(CO)(2)B(N(i)Pr(2))Cl (7a) are reported. Compound 2ais shown to be a versatile substrate for further boron-centred substitution chemistry leading to the asymmetric boryl complexes (eta(5)-C(5)H(5))Fe(CO)(2)B(OMes)ER(n) [ER(n) = OC(6)H(4)(t)Bu-4, 2c; ER(n) = SPh, 2d] with retention of the metal-boron bond. The reactivities of 2a, 3a and 7a towards the halide abstraction agent Na[BAr(f)(4)] have also been examined, in order to investigate the potential for the generation of cationic heteroatom-stabilized terminal borylene complexes. The application of this methodology to the mesityloxy derivatives and gives rise to B-F containing products, presumably via fluoride abstraction from the [BAr(f)(4)](-) counter-ion. By contrast, amino-functionalized complex 7a is more amenable to this approach, and the thermally robust terminal aminoborylene complex [(eta(5)-C(5)H(5))Fe(CO)(2)B(N(i)Pr(2))][BAr(f)(4)] (9) can be isolated in ca. 50% yield. The reactivity of 9towards a range of nucleophilic and/or unsaturated reagents has been examined, with examples of addition, protonolysis and metathesis chemistries having been established. |
|---|---|
| Language | English |
| Publishing date | 2006-01-14 |
| Publishing country | England |
| Document type | Journal Article |
| ZDB-ID | 1472887-4 |
| ISSN | 1364-5447 ; 1477-9234 ; 1477-9226 ; 0300-9246 |
| ISSN (online) | 1364-5447 ; 1477-9234 |
| ISSN | 1477-9226 ; 0300-9246 |
| DOI | 10.1039/b512275a |
| Database | MEDical Literature Analysis and Retrieval System OnLINE |
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