Construction of Rhodium(I) and Gold(I) Macrocycles by Transferring a Phosphine-Functionalized 4,5-Diazafluorenide Ligand from Its Copper(I) N-Heterocyclic Carbene Complex

被引：18

作者：

Tan, Runyu ^{[1
]}

Chiu, Frederick Sin Nang ^{[1
]}

Hadzovic, Alen ^{[1
]}

Song, Datong ^{[1
]}

机构：

[1] Univ Toronto, Dept Chem, Davenport Chem Res Labs, Toronto, ON M5S 3H6, Canada

来源：

ORGANOMETALLICS | 2012年 / 31卷 / 06期

基金：

加拿大自然科学与工程研究理事会;

关键词：

CRYSTAL-STRUCTURE; COORDINATION; DERIVATIVES;

D O I：

10.1021/om200994b

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

We report the synthesis and characterization of a phosphine-functionalized 4,5-diazafluorene ligand, 9-(2-(diphenylphosphino)ethyl)-4,5-diazafluorene (LpH), and its Cu(IPr) complex (IPr = N,M-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene) [Cu(IPr)L-p] (2a), which exhibits a monomeric structure in solution but dimerizes in the solid state. Compound 2a reacts with Rh(PPh3)(3)Cl, [Rh(COD)-Cl](2), Au(SMe2)Cl, and Au(IPr)Cl to form the macrocyclic complexes [Rh(PPh3)Lp](2) (2b), [Rh(COD)L-p](2) (2c), and [AuLp](2) (2d) and the mononuclear complex [Au(IPr)L-p] (2f), respectively, via ligand transfer. Although 2b-d,f could also be synthesized from the deprotonated ligand L-p(-) and the corresponding metal starting materials directly, the reactions require longer time and give lower yields. The reaction between LpH and Au(SMe2)Cl gives Au(LpH)(2)Cl (2e) exclusively.

引用

页码：2184 / 2192

页数：9

共 25 条

[1] Modular construction of a series of heteronuclear metallamacrocycles [J].

Baudron, Stephane A. ;

Hosseini, Mir Wais .

CHEMICAL COMMUNICATIONS, 2008, (38) :4558-4560

[2]

Baudron SA, 2007, DALTON T, P1129, DOI 10.1039/b616841h

[3] Evolution of organo-cyanometallate cages:: Supramolecular architectures and new Cs+-specific receptors [J].

Boyer, Julie L. ;

Kuhlman, Matthew L. ;

Rauchfuss, Thomas B. .

ACCOUNTS OF CHEMICAL RESEARCH, 2007, 40 (04) :233-242

[4] Luminescent gold(I) macrocycles with diphosphine and 4,4′-bipyridyl ligands [J].

Brandys, MC ;

Jennings, MC ;

Puddephatt, RJ .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2000, (24) :4601-4606

[5]

*BRUK AXS INC, 2008, AP 2 SOFTW PACK

[6] Supermolecules by design [J].

Caulder, DL ;

Raymond, KN .

ACCOUNTS OF CHEMICAL RESEARCH, 1999, 32 (11) :975-982

[7]

Crabtree R., 2006, COMPREHENSIVE ORGAN

[8] Synthesis and structural characterization of N-heterocyclic carbene gold(I) complexes [J].

de Frémont, P ;

Scott, NM ;

Stevens, ED ;

Nolan, SP .

ORGANOMETALLICS, 2005, 24 (10) :2411-2418

[9] [(NHC)CuX] complexes: Synthesis, characterization and catalytic activities in reduction reactions and Click Chemistry. On the advantage of using well-defined catalytic systems [J].

Diez-Gonzalez, Silvia ;

Escudero-Adan, Eduardo C. ;

Benet-Buchholz, Jordi ;

Stevens, Edwin D. ;

Slawin, Alexandra M. Z. ;

Nolan, Steven P. .

DALTON TRANSACTIONS, 2010, 39 (32) :7595-7606

[10] Copper N-heterocyclic carbene (NHC) complexes as carbene transfer reagents [J].

Furst, Marc R. L. ;

Cazin, Catherine S. J. .

CHEMICAL COMMUNICATIONS, 2010, 46 (37) :6924-6925

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