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Site selectivity and reversibility in the reactions of titanium hydrazides with Si-H, Si-X, C-X and H+ reagents: Ti=N(α) 1,2-silane addition, Nβ alkylation, Nα protonation and σ-bond metathesis.

Abstract:

We report a combined experimental and computational comparative study of the reactions of the homologous titanium dialkyl- and diphenylhydrazido and imido compounds Cp*Ti{MeC(N(i)Pr)(2)}(NNR(2)) (R = Me (1) or Ph (2)) and Cp*Ti{MeC(N(i)Pr)(2)}(NTol) (3) with silanes, halosilanes, alkyl halides and [Et(3)NH][BPh(4)]. Compound 1 underwent reversible Si-H 1,2-addition to Ti=N(α) with RSiH(3) (experimental ΔH ca. -17 kcal mol(-1)), and irreversible addition with PhSiH(2)X (X = Cl, Br). DFT found ...

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Publication status:
Published

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Publisher copy:
10.1039/c2dt12359b

Authors


Schwarz, AD More by this author
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Journal:
Dalton transactions (Cambridge, England : 2003)
Volume:
41
Issue:
8
Pages:
2277-2288
Publication date:
2012-02-05
DOI:
EISSN:
1477-9234
ISSN:
1477-9226
URN:
uuid:690dee5f-2254-4f05-86a0-c7a978f4e605
Source identifiers:
237038
Local pid:
pubs:237038

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