Syntheses, structure, and molecular cubic hyperpolarizabilities of systematically varied ethynylgold(I) complexes

José Vicente; María Teresa Chicote; María Dolores Abrisqueta; M. Carmen Ramírez de Arellano; Peter G. Jones; Mark G. Humphrey; Marie P. Cifuentes; Marek Samoc; Barry Luther-Davies

doi:10.1021/om000093t

Syntheses, structure, and molecular cubic hyperpolarizabilities of systematically varied ethynylgold(I) complexes

José Vicente^*, María Teresa Chicote, María Dolores Abrisqueta, M. Carmen Ramírez de Arellano, Peter G. Jones, Mark G. Humphrey, Marie P. Cifuentes, Marek Samoc, Barry Luther-Davies

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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Abstract

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 complexes Q[Au(C=CC₆H₄R-4)₂] (R = NO₂ (1), C₆H₄NO₂-4 (2), (E)-CH=CHC₆H₄NO₂-4 (3)). The same alkynes react with [AuCl(CNBu^t)] in NEt₃ to give the complexes [Au(C=CC₆H₄R-4)(CNBu_t)] (R = NO₂ (4), C₆H₄NO₂-4 (5), (E)-CH=CHC₆H₄NO₂-4 (6)). When NHEt₂ is used instead of NEt₃, attack of the secondary amine at the isonitrile ligand takes place and alkynyl carbene complexes of the type [Au(C=CC₆H₄R-4){C(NHBu^t)(NEt₂)}] (R = NO₂ (7), C₆H₄NO₂-4 (8), (E)-CH=CHC₆H₄NO₂-4 (9)) are obtained. The crystal structures of 1a, 4, 7, and 9 have been determined. The cubic hyperpolarizabilities of 1a,b, 4-6, 8, 9, and the related complexes [Au(C=CC₆H₄R-4)(PPh₃)] (R = H (10), NO₂ (11), 4-C₆H₄NO₂ (12), (E)-CH=CHC₆H₄NO₂-4 (13), C=CC₆H₄NO₂-4 (14), (Z)-CH=CHC₆H₄NO₂-4 (15), (S)-N=CHC₆H₄NO₂-4 (16)) have been determined by Z-scans at 800 nm. An increase in γ_real is observed on replacing the coligand Bu^tNC 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 π-bridge (proceeding from 11 to 12-15), and replacing (Z)-CH=CH by the (E)-CH=CH linking unit (proceeding from 15 to 13).

Original language	English
Pages (from-to)	2968-2974
Number of pages	7
Journal	Organometallics
Volume	19
Issue number	16
DOIs	https://doi.org/10.1021/om000093t
Publication status	Published - 7 Aug 2000

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@article{db32e5a120cf405494961d38180b8db0,

title = "Syntheses, structure, and molecular cubic hyperpolarizabilities of systematically varied ethynylgold(I) complexes",

abstract = "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 complexes Q[Au(C=CC6H4R-4)2] (R = NO2 (1), C6H4NO2-4 (2), (E)-CH=CHC6H4NO2-4 (3)). The same alkynes react with [AuCl(CNBut)] in NEt3 to give the complexes [Au(C=CC6H4R-4)(CNBut)] (R = NO2 (4), C6H4NO2-4 (5), (E)-CH=CHC6H4NO2-4 (6)). When NHEt2 is used instead of NEt3, attack of the secondary amine at the isonitrile ligand takes place and alkynyl carbene complexes of the type [Au(C=CC6H4R-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 been determined. The cubic hyperpolarizabilities of 1a,b, 4-6, 8, 9, and the related complexes [Au(C=CC6H4R-4)(PPh3)] (R = H (10), NO2 (11), 4-C6H4NO2 (12), (E)-CH=CHC6H4NO2-4 (13), C=CC6H4NO2-4 (14), (Z)-CH=CHC6H4NO2-4 (15), (S)-N=CHC6H4NO2-4 (16)) have been determined by Z-scans at 800 nm. An increase in γreal is observed on replacing the coligand ButNC 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 π-bridge (proceeding from 11 to 12-15), and replacing (Z)-CH=CH by the (E)-CH=CH linking unit (proceeding from 15 to 13).",

author = "Jos{\'e} Vicente and {Teresa Chicote}, Mar{\'i}a and {Dolores Abrisqueta}, Mar{\'i}a and {Carmen Ram{\'i}rez de Arellano}, M. and Jones, {Peter G.} and Humphrey, {Mark G.} and Cifuentes, {Marie P.} and Marek Samoc and Barry Luther-Davies",

year = "2000",

month = aug,

day = "7",

doi = "10.1021/om000093t",

language = "English",

volume = "19",

pages = "2968--2974",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "16",

}

TY - JOUR

T1 - Syntheses, structure, and molecular cubic hyperpolarizabilities of systematically varied ethynylgold(I) complexes

AU - Vicente, José

AU - Teresa Chicote, María

AU - Dolores Abrisqueta, María

AU - Carmen Ramírez de Arellano, M.

AU - Jones, Peter G.

AU - Humphrey, Mark G.

AU - Cifuentes, Marie P.

AU - Samoc, Marek

AU - Luther-Davies, Barry

PY - 2000/8/7

Y1 - 2000/8/7

N2 - 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 complexes Q[Au(C=CC6H4R-4)2] (R = NO2 (1), C6H4NO2-4 (2), (E)-CH=CHC6H4NO2-4 (3)). The same alkynes react with [AuCl(CNBut)] in NEt3 to give the complexes [Au(C=CC6H4R-4)(CNBut)] (R = NO2 (4), C6H4NO2-4 (5), (E)-CH=CHC6H4NO2-4 (6)). When NHEt2 is used instead of NEt3, attack of the secondary amine at the isonitrile ligand takes place and alkynyl carbene complexes of the type [Au(C=CC6H4R-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 been determined. The cubic hyperpolarizabilities of 1a,b, 4-6, 8, 9, and the related complexes [Au(C=CC6H4R-4)(PPh3)] (R = H (10), NO2 (11), 4-C6H4NO2 (12), (E)-CH=CHC6H4NO2-4 (13), C=CC6H4NO2-4 (14), (Z)-CH=CHC6H4NO2-4 (15), (S)-N=CHC6H4NO2-4 (16)) have been determined by Z-scans at 800 nm. An increase in γreal is observed on replacing the coligand ButNC 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 π-bridge (proceeding from 11 to 12-15), and replacing (Z)-CH=CH by the (E)-CH=CH linking unit (proceeding from 15 to 13).

AB - 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 complexes Q[Au(C=CC6H4R-4)2] (R = NO2 (1), C6H4NO2-4 (2), (E)-CH=CHC6H4NO2-4 (3)). The same alkynes react with [AuCl(CNBut)] in NEt3 to give the complexes [Au(C=CC6H4R-4)(CNBut)] (R = NO2 (4), C6H4NO2-4 (5), (E)-CH=CHC6H4NO2-4 (6)). When NHEt2 is used instead of NEt3, attack of the secondary amine at the isonitrile ligand takes place and alkynyl carbene complexes of the type [Au(C=CC6H4R-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 been determined. The cubic hyperpolarizabilities of 1a,b, 4-6, 8, 9, and the related complexes [Au(C=CC6H4R-4)(PPh3)] (R = H (10), NO2 (11), 4-C6H4NO2 (12), (E)-CH=CHC6H4NO2-4 (13), C=CC6H4NO2-4 (14), (Z)-CH=CHC6H4NO2-4 (15), (S)-N=CHC6H4NO2-4 (16)) have been determined by Z-scans at 800 nm. An increase in γreal is observed on replacing the coligand ButNC 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 π-bridge (proceeding from 11 to 12-15), and replacing (Z)-CH=CH by the (E)-CH=CH linking unit (proceeding from 15 to 13).

UR - http://www.scopus.com/inward/record.url?scp=0000776091&partnerID=8YFLogxK

U2 - 10.1021/om000093t

DO - 10.1021/om000093t

M3 - Article

SN - 0276-7333

VL - 19

SP - 2968

EP - 2974

JO - Organometallics

JF - Organometallics

IS - 16

ER -

Syntheses, structure, and molecular cubic hyperpolarizabilities of systematically varied ethynylgold(I) complexes

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