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Reactivity of Cationic Dinitrosyl Bisphosphine Rhenium Complexes toward Acetylene: Base-Controlled Product Formation


Berke, H; Frech, C M; Llamazares, A; Blacque, O; Schmalle, H W (2009). Reactivity of Cationic Dinitrosyl Bisphosphine Rhenium Complexes toward Acetylene: Base-Controlled Product Formation. Organometallics, 18(28):5333-5340.

Abstract

Reactions of the dinitrosyl bisphosphine rhenium cations [Re(NO)2(PR3)2][BArF4] (R = Cy 1a; R = iPr 1b; [BArF4]− = tetrakis[(3,5-bis(trifluoromethyl)phenyl)borate]) with acetylene yielded the alkynyl (o-vinyl)hydroxylamido nitrosyl bisphosphine complexes [Re(CH═C(H)ONH)(C≡CH)(NO)(PR3)2][BArF4] (3a and 3b) in the absence of base, while in the presence of 2,6-di(tert-butyl)pyridine formation of the neutral alkynyl complexes [Re(C≡CH)(NO)2(PR3)2] (4a and 4b) was observed. A plausible mechanism is presented and supported by various NMR techniques, IR spectroscopy, and DFT calculations. Treatment of 4a and 4b with [H(OEt2)2][BArF4] gave the corresponding vinylidene complexes [Re(C═CH2)(NO)2(PR3)2][BArF4] (5a and 5b) in high yields, which only slowly convert into the alkynyl(o-vinyl)hydroxylamido nitrosyl bisphosphine complexes 3a and 3b when treated with a large excess of acetylene. Thiophenol or benzeneselenol underwent 1,2-additions onto the vinylidene ligands of 5a and 5b to yield the cationic Fischer-type carbene complexes [Re(C(XPh)CH3)(NO)2(PR3)2][BArF4] (X = S 6a,b; X = Se 7a,b) quantitatively. X-ray diffraction studies were carried out on 4b, 5b, and 7a.

Reactions of the dinitrosyl bisphosphine rhenium cations [Re(NO)2(PR3)2][BArF4] (R = Cy 1a; R = iPr 1b; [BArF4]− = tetrakis[(3,5-bis(trifluoromethyl)phenyl)borate]) with acetylene yielded the alkynyl (o-vinyl)hydroxylamido nitrosyl bisphosphine complexes [Re(CH═C(H)ONH)(C≡CH)(NO)(PR3)2][BArF4] (3a and 3b) in the absence of base, while in the presence of 2,6-di(tert-butyl)pyridine formation of the neutral alkynyl complexes [Re(C≡CH)(NO)2(PR3)2] (4a and 4b) was observed. A plausible mechanism is presented and supported by various NMR techniques, IR spectroscopy, and DFT calculations. Treatment of 4a and 4b with [H(OEt2)2][BArF4] gave the corresponding vinylidene complexes [Re(C═CH2)(NO)2(PR3)2][BArF4] (5a and 5b) in high yields, which only slowly convert into the alkynyl(o-vinyl)hydroxylamido nitrosyl bisphosphine complexes 3a and 3b when treated with a large excess of acetylene. Thiophenol or benzeneselenol underwent 1,2-additions onto the vinylidene ligands of 5a and 5b to yield the cationic Fischer-type carbene complexes [Re(C(XPh)CH3)(NO)2(PR3)2][BArF4] (X = S 6a,b; X = Se 7a,b) quantitatively. X-ray diffraction studies were carried out on 4b, 5b, and 7a.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:3 September 2009
Deposited On:13 Oct 2009 14:20
Last Modified:05 Apr 2016 13:21
Publisher:American Chemical Society
ISSN:0276-7333
Publisher DOI:10.1021/om9003412
Official URL:http://pubs.acs.org
Permanent URL: http://doi.org/10.5167/uzh-20811

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