Synthesis and characterization of a free phenylene bis(N-heterocyclic carbene) and its di-Rh complex: Catalytic activity of the di-Rh and CCC–NHC Rh pincer complexes in intermolecular hydrosilylation of alkynes

Andavan, Gurusamy Thangavelu Senthil; Bauer, Eike B.; Letko, Christopher S.; Hollis, T. Keith; Tham, Fook S.

doi:10.1016/j.jorganchem.2005.07.088

Cited by 93 publications

(49 citation statements)

References 77 publications

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“…3,170.8 (J RhC ¼ 58.8 Hz) and 157.7 ppm, respectively. These carbene signals have the same chemical shifts as those for previously reported neutral Cp* iridium(III) and rhodium(III) complexes bearing a monodentate N-heterocyclic carbene ligand [6,8].…”

Section: Synthesis Of Imidazolium Salts and Binuclear Neutral Iridiummentioning

confidence: 98%

“…124. 3,125.6,126.8,128.8,132.2,133.9,137.7,137.9 (s,CH]CH, naphthalene,), 167.5 (d,J ¼ 58.8 Hz,NCN). 31 P{ 1 H} NMR (CDCl 3 ): d À143.8 (sep, J ¼ 713 Hz, PF 6 ).…”

Section: Preparation Of [(Cp*ircl 2 ) 2 (I I Prch 2 C 10 H 6 Ch 2 I Imentioning

confidence: 99%

“…The use of chelating bis-NHC and pincer NHC ligands has allowed for the preparation of new complexes which show increased catalytic activity [2] along with improved stability due to the entropic advantages of chelation. In contrast to chelated NHC complexes, the reactivity and catalytic application of binuclear bridging NHC complex has scarcely been studied [3] even though several binuclear complexes with alkyl chain-linked NHC ligand have been prepared [4]. In order to bring the metals together such that cooperative interaction is possible, the bridging NHC complex needs to have short metalemetal separation.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of binuclear iridium(III) and rhodium(III) complexes bearing methylnaphthalene-linked N-heterocyclic carbenes, and application to intramolecular hydroamination

Ogata

Nagaya

Fukuzawa

2010

Journal of Organometallic Chemistry

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Section: Synthesis Of Imidazolium Salts and Binuclear Neutral Iridiummentioning

confidence: 98%

“…124. 3,125.6,126.8,128.8,132.2,133.9,137.7,137.9 (s,CH]CH, naphthalene,), 167.5 (d,J ¼ 58.8 Hz,NCN). 31 P{ 1 H} NMR (CDCl 3 ): d À143.8 (sep, J ¼ 713 Hz, PF 6 ).…”

Section: Preparation Of [(Cp*ircl 2 ) 2 (I I Prch 2 C 10 H 6 Ch 2 I Imentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of binuclear iridium(III) and rhodium(III) complexes bearing methylnaphthalene-linked N-heterocyclic carbenes, and application to intramolecular hydroamination

Ogata

Nagaya

Fukuzawa

2010

Journal of Organometallic Chemistry

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“…Bis(imidazolin-2-ylidenes) and diimidazolium salts. (83), [171] lutidine-(84), [172] and phenylene-bridged (85 [173] and 86 [172a,c,d] ) bis(imidazolin-2-ylidenes) are known in addition to the diethyl amine bridged ligand 87.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…Angewandte Chemie donor groups. Today pyridine-(83), [171] lutidine-(84), [172] and phenylene-bridged (85 [173] and 86 [172a,c,d] ) bis(imidazolin-2ylidenes) are known in addition to the diethyl amine bridged ligand 87. [174] Often, the free ligands were not isolated but generated in situ by deprotonation of the diimidazolium salts.…”

Section: Heterocyclic Carbenesmentioning

confidence: 99%

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

2008

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The chemistry of heterocyclic carbenes has experienced a rapid development over the last years. In addition to the imidazolin-2-ylidenes, a large number of cyclic diaminocarbenes with different ring sizes have been described. Aside from diaminocarbenes, P-heterocyclic carbenes, and derivatives with only one, or even no heteroatom within the carbene ring are known. New methods for the synthesis of complexes with N-heterocyclic carbene ligands such as the oxidative addition or the metal atom template controlled cyclization of beta-functionalized isocyanides have been developed recently. This review summarizes the new developments regarding the synthesis of N-heterocyclic carbenes and their metal complexes.

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The Nature of N‐Heterocyclic Carbenes

Kühl

2010

Functionalised N‐Heterocyclic Carbene Complexes

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There are essentially three different types of transition metal carbene complexes featuring three different types of carbene ligands. They have all been named after their fi rst discoverers: Fischer carbenes [ 27 -29 ], Schrock carbenes [ 30 , 31 ] and Wanzlick -Arduengo carbenes (see Figure 1.1 ). The latter, also known as N -heterocyclic carbenes (NHC), should actually be named after three people: Ö fele [ 2 ] and Wanzlick [ 3 ], who independently synthesised their fi rst transition metal complexes in 1968, and Arduengo [ 1 ] who reported the fi rst free and stable NHC in 1991. Fischer carbene complexes have an electrophilic carbene carbon atom [ 32 ] that can be attacked by a Lewis base. The Schrock carbene complex has a reversed reactivity. The Schrock carbene complex is usually employed in olefi n metathesis (Grubbs ' catalyst) or as an alternative to phosphorus ylides in the Wittig reaction [ 33 ].The NHC are different from both other types. They form transition metal complexes that are essentially inert, although exceptions are known. Their exceptional stability derives from their intrinsic stabilisation from the N -C p π -p π bonding interaction of the nitrogen atoms fl anking the carbene carbon atom. The p orbital of the carbon is thus partially fi lled and no longer available for nucleophilic attack. Also, it does not have a lone pair of its own with which it could possibly engage in a nucleophilic interaction of its own. Hence, it remains unreactive taking the middle ground between the opposing reactivities of Fischer and Schrock carbenes. It is this apparent lack of reactivity that meant that the transition metal NHC complexes received little attention in their early history. Functionalised N-Heterocyclic Carbene ComplexesOlaf Kühl

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Synthesis and characterization of a free phenylene bis(N-heterocyclic carbene) and its di-Rh complex: Catalytic activity of the di-Rh and CCC–NHC Rh pincer complexes in intermolecular hydrosilylation of alkynes

Cited by 93 publications

References 77 publications

Synthesis of binuclear iridium(III) and rhodium(III) complexes bearing methylnaphthalene-linked N-heterocyclic carbenes, and application to intramolecular hydroamination

Synthesis of binuclear iridium(III) and rhodium(III) complexes bearing methylnaphthalene-linked N-heterocyclic carbenes, and application to intramolecular hydroamination

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

The Nature of N‐Heterocyclic Carbenes

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