Syntheses, Structure, and Molecular Cubic Hyperpolarizabilities of Systematically Varied Ethynylgold(I) Complexes
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- 作者：José ; Vicente ; Marí ; a Teresa Chicote ; Marí ; a Dolores Abrisqueta ; M. Carmen Ramí ; rez de Arellano ; Peter G. Jones ; Mark G. Humphrey ; Marie P. Cifuentes ; Marek Samoc ; and Barry Lu
- 刊名：Organometallics
- 出版年：2000
- 出版时间：August 7, 2000
- 年：2000
- 卷：19
- 期：16
- 页码：2968 - 2974
- 全文大小：149K
- 年卷期：v.19,no.16(August 7, 2000)
- ISSN：1520-6041
文摘
The reactions of Q[Au(acac)2] (Q = N(PPh3)2 (PPN; a), NPr4 (b); acac = acetylacetonato)with terminal alkynes of the type HC
CC6H4R-4 in a 1:2 molar ratio affords the complexesQ[Au(CCC6H4R-4)2] (R = NO2 (1), C6H4NO2-4 (2), (E)-CH=CHC6H4NO2-4 (3)). The samealkynes react with [AuCl(CNBut)] in NEt3 to give the complexes [Au(CCC6H4R-4)(CNBut)](R = NO2 (4), C6H4NO2-4 (5), (E)-CH=CHC6H4NO2-4 (6)). When NHEt2 is used instead ofNEt3, attack of the secondary amine at the isonitrile ligand takes place and alkynyl carbenecomplexes of the type [Au(CCC6H4R-4){C(NHBut)(NEt2)}] (R = NO2 (7), C6H4NO2-4 (8),(E)-CH=CHC6H4NO2-4 (9)) are obtained. The crystal structures of 1a, 4, 7, and 9 have beendetermined. The cubic hyperpolarizabilities of 1a,b, 4-6, 8, 9, and the related complexes[Au(CCC6H4R-4)(PPh3)] (R = H (10), NO2 (11), 4-C6H4NO2 (12), (E)-CH=CHC6H4NO2-4(13), CCC6H4NO2-4 (14), (Z)-CH=CHC6H4NO2-4 (15), (E)-N=CHC6H4NO2-4 (16)) have beendetermined by Z-scans at 800 nm. An increase in 
real is observed on replacing the coligandButNC by PPh3 (proceeding from 5 to 12 and from 6 to 13), introduction of the NO2 group(proceeding from 10 to 11), extending the arylalkynyl 
-bridge (proceeding from 11 to 12-15), and replacing (Z)-CH=CH by the (E)-CH=CH linking unit (proceeding from 15 to 13).
CC6H4R-4 in a 1:2 molar ratio affords the complexesQ[Au(CCC6H4R-4)2] (R = NO2 (1), C6H4NO2-4 (2), (E)-CH=CHC6H4NO2-4 (3)). The samealkynes react with [AuCl(CNBut)] in NEt3 to give the complexes [Au(CCC6H4R-4)(CNBut)](R = NO2 (4), C6H4NO2-4 (5), (E)-CH=CHC6H4NO2-4 (6)). When NHEt2 is used instead ofNEt3, attack of the secondary amine at the isonitrile ligand takes place and alkynyl carbenecomplexes of the type [Au(CCC6H4R-4){C(NHBut)(NEt2)}] (R = NO2 (7), C6H4NO2-4 (8),(E)-CH=CHC6H4NO2-4 (9)) are obtained. The crystal structures of 1a, 4, 7, and 9 have beendetermined. The cubic hyperpolarizabilities of 1a,b, 4-6, 8, 9, and the related complexes[Au(CCC6H4R-4)(PPh3)] (R = H (10), NO2 (11), 4-C6H4NO2 (12), (E)-CH=CHC6H4NO2-4(13), CCC6H4NO2-4 (14), (Z)-CH=CHC6H4NO2-4 (15), (E)-N=CHC6H4NO2-4 (16)) have beendetermined by Z-scans at 800 nm. An increase in real is observed on replacing the coligandButNC by PPh3 (proceeding from 5 to 12 and from 6 to 13), introduction of the NO2 group(proceeding from 10 to 11), extending the arylalkynyl -bridge (proceeding from 11 to 12-15), and replacing (Z)-CH=CH by the (E)-CH=CH linking unit (proceeding from 15 to 13).