Eine einfache synthese von tripod-liganden H3CC(CH2PAr2)3: Anwendungsbreite und komplexchemie

Muth, A.; Walter, Olaf; Hüttner, Gottfried; Asam, A.; Zsolnai, László; Emmerich, Christiane

doi:10.1016/0022-328x(94)80044-8

Cited by 45 publications

(23 citation statements)

References 35 publications

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“…The tripodal phosphine 1,1,1-tris(diphenylphosphinomethyl)ethane (CH 3 (CH 2 PPh 2 ) 3 , triphos, 1) is one of the most widely studied triphosphine ligands and has been shown to form an extensive range of metal complexes [4][5][6][7][8][9][10][11][12] and a number of active catalytic species [13][14][15][16][17][18]. New triphos-type ligands continue to attract interest for the preparation of coordination complexes [19][20][21][22][23][24], however, their synthesis is not always trivial. Triphos ligands are commonly prepared via the nucleophilic substitution of a suitable alkyltrihalide backbone with a dialkyl/diaryl phosphide generated from the corresponding secondary phosphine.…”

Section: Introductionmentioning

confidence: 99%

The preparation of multimetallic complexes using sterically bulky N-centred tripodal dialkyl phosphino ligands

Miller

White

2010

Journal of Organometallic Chemistry

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Section: Introductionmentioning

confidence: 99%

The preparation of multimetallic complexes using sterically bulky N-centred tripodal dialkyl phosphino ligands

Miller

White

2010

Journal of Organometallic Chemistry

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“…[11] This synthetic pathway involved the substitution of 1,1,1-tris-(chloromethyl)ethane with an in situ prepared solution of ad eprotonated secondary aryl phosphine in DMSO.T his procedure was successfully employed in the preparation of the triphos-derivatives, L2 and L3,i nw hich the reaction conditions were dependent on the nature of the phosphine nucleophile.…”

Section: Zuschriftenmentioning

confidence: 99%

Tailor‐Made Ruthenium‐Triphos Catalysts for the Selective Homogeneous Hydrogenation of Lactams

et al. 2015

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The development of at ailored tridentate ligand enabled the synthesis of am olecular ruthenium-triphos catalyst, eliminating dimerization as the major deactivation pathway.T he novel catalyst design showed strongly increased performance and facilitated the hydrogenation of highly challenging lactam substrates with unprecedented activity and selectivity.Catalytic hydrogenation using molecular catalysts based on defined organometallic complexes has been advanced to be an essential tool for the chemical synthesis in research laboratories as well as on the industrial scale.[1] Very effective catalysts could be tailored for the addition of hydrogen to complex organic substrates,l argely based on fundamental mechanistic insight on am olecular level. Moreover,r ecent research efforts have illustrated that ruthenium complexes of the multidentate triphos (1,1,1-tri(diphenylphosphinomethyl)ethane) ligand demonstrate potential for the development of highly active and stable homogeneous species.[2] Especially for the reduction of challenging functionalities, the ruthenium-triphos systems could be established as important molecular catalyst, [2b,c] finding increasing application in numerous research groups.[3] This important advancement moved these molecular catalysts into the spotlight for novel transformations and in special cases closer to processing conditions of heterogeneous catalyst systems.[4] Nevertheless,t he hydrogenation of non-activated aliphatic amides remains an enormous challenge for molecular catalysts and especially the reductive cleavage of lactams requires novel dedicated catalysts.T he group of Bergens introduced the catalyst [Ru(Ph 2 P(CH 2 ) 2 NH 2 ) 2 (m 3 -C 3 H 5 )]BF 4 for the hydrogenation of N-phenylpyrrolidin-2-one,e nabling the formation of the respective amino alcohol with CÀNc leavage with high turnover number (TON).[5] Most recently the group of Milstein presented N,N,P-pincer ruthenium complexes for the conversion of glycine anhydride into ethanolamine in high yield.[6] Ther eduction of lactams to cyclic amines is still demanding,b ut the groups of Mashima and Saito could already use ab is-bidentate (P,N) 2 -Ru system to accomplish this transformation and obtained the cyclic products in low to moderate yield.[7] Therefore,effective homogeneous catalysts for the hydrogenolysis of lactams towards cyclic amines remain largely elusive and the development of novel transition-metal compounds for this challenging catalytic transformation needs to be established. Herein we describe arationally developed novel triphos-type ligand that enables this transformation in hitherto unprecedented efficacy.In our recent effort we could establish the highly versatile and stable ruthenium complex [Ru(triphos)(tmm)] (1a, tmm = trimethylenemethane)a sa ctive catalysts system. [2c,8] Initial mechanistic evaluation of the active hydride species 1b revealed two reaction pathways as important targets for tailoring an improved catalyst (Scheme 1).[ [2a] Them ajor pathway results in deactivation and is b...

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“…[13] [14] [15] [16] When this work was commenced, nine relevant structure determinations had been reported [17] referring to ten crystallographically independent molecules of this type. To illustrate the overall structural characteristics of this type of compound, Figure 1 shows two mutually orthogonal projections of the structure of CH 3 C-(CH 2 PPh 2 ) 3 Mo(CO) 3 .…”

Section: Data Basismentioning

confidence: 99%

“…[13] [14] [15] [16] The structures of a number of such compounds have been determined by X-ray crystallography.…”

Section: Data Basismentioning

confidence: 99%

How to Derive Force Field Parameters by Genetic Algorithms: Modellingtripod-Mo(CO)3 Compounds as an Example

Hunger

Beyreuther

Hüttner

et al. 1998

Eur. J. Inorg. Chem.

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Eine einfache synthese von tripod-liganden H3CC(CH2PAr2)3: Anwendungsbreite und komplexchemie

Cited by 45 publications

References 35 publications

The preparation of multimetallic complexes using sterically bulky N-centred tripodal dialkyl phosphino ligands

The preparation of multimetallic complexes using sterically bulky N-centred tripodal dialkyl phosphino ligands

Tailor‐Made Ruthenium‐Triphos Catalysts for the Selective Homogeneous Hydrogenation of Lactams

How to Derive Force Field Parameters by Genetic Algorithms: Modellingtripod-Mo(CO)3 Compounds as an Example

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