Rhodium pincer complexes of 2,2′-bis(diphenylphosphino)diphenylamine

Winter, Angelika M.; Eichele, Klaus; Mack, Hans‐Georg; Potuznik, Suzan; Mayer, Hermann A.; Kaska, William C.

doi:10.1016/s0022-328x(03)00776-9

Cited by 85 publications

(50 citation statements)

References 26 publications

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“…The amide nitrogen of the ene-hydrazone ligand is a weaker pacceptor, therefore due to the increasing electron density on the metal a reduction of the value of carbonyl valence vibration from 6 to 34 cm À1 was observed between pairs of corresponding complexes 5 and 9, 6 and 10, etc. The value of 1957 cm À1 for complex 9 is close to the value of 1960 cm À1 found by Mayer and Kaska [6] for the only rhodium PNP pincer amido carbonyl complex known so far. Significant further increase of electron density on rhodium was achieved by substituting phenyl groups on phosphorus atoms by more electron-donating groups, the value of carbonyl valence vibration for the tert-butyl substituted complex being 1938 cm À1 .…”

supporting

confidence: 86%

“…Therefore two different signals of methylene protons were observed for complexes 5-8 and in complexes 9-12 only one signal of the methylene protons and one signal of methine proton was observed. Depending on the particular complex these signals were doublets (6) or doublets of doublets (5,7,8) with very well resolved 2 J PH and 4 J PH ; signal of methine proton in complexes 9-12 was doublet of doublets in all the cases.…”

mentioning

confidence: 92%

“…287], but the first rhodium amido carbonyl pincer complex was reported by Mayer and Kaska [6] only recently.…”

Section: Introductionmentioning

confidence: 99%

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Square planar diphosphinoazine rhodium(I) amido carbonyl complexes with an unsymmetrical PNP′ pincer-type coordination

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confidence: 86%

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confidence: 92%

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Square planar diphosphinoazine rhodium(I) amido carbonyl complexes with an unsymmetrical PNP′ pincer-type coordination

Pošta

Čermák

Sýkora

et al. 2008

Journal of Organometallic Chemistry

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“…1 [20]. The first such ligand to be described, namely [PNP Ph ], features phenyl substituents on phosphorus and was reported independently by two research groups in 2003 [21,22] [25,26] as illustrated in Scheme 1, i.e. sequential treatment of (2-Br, 4-Me-C 6 H 3 ) 2 NH with (i) Bu n Li, (ii) Ph 2 PCl and (iii) HCl.…”

Section: [J 2 -{[Mepnp Ph ]H}gabr 2 ][Gabrmentioning

confidence: 99%

“…1 [20]. The first such ligand to be described, namely [PNP Ph ], features phenyl substituents on phosphorus and was reported independently by two research groups in 2003 [21,22]. Shortly thereafter, derivatives that possess cyclohexyl, isopropyl and isobutyl substituents on phosphorus, namely [PNP Cy ] [23], [PNP Pr i ] [23] and [PNP Bu i ] [24], were reported, together with a variant that possesses a tolylene linker, [MePNP Pr i ] [25-27].…”

mentioning

confidence: 99%

Gallium and indium compounds supported by a [PNP] pincer ligand

Yurkerwich

Parkin

2010

Inorganica Chimica Acta

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Cleavage of Nitrogen–Hydrogen Bonds of Ammonia Induced by Triruthenium Polyhydrido Clusters

2006

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NÀH bond activation of amines has attracted increasing attention owing to its applicability to the synthesis of various amino compounds, and the development of a new and effective reaction system for the activation of ammonia must be one of the most important research targets in connection with the transformation of abundant and inexpensive ammonia into a useful amino compound.[1] However, successful examples of activation of the NÀH bond of ammonia are still rare because of both the high NÀH bond dissociation energy ( % 104 AE 2 kcal mol À1 ) [2] and the difficulty in forming an NÀH s complex.[3]The groups of Milstein [1g, i, j] and Hartwig [1k, q] showed independently that some mononuclear iridium(i) complexes exhibited activity towards oxidative addition of ammonia. A highly unsaturated 14 e species with T-shaped geometry was proposed as a reactive intermediate for the NÀH bond cleavage on the basis of kinetic studies.[1q] Some complexes containing a d 0 metal center, such as [Cp* 2 MH 2 ] (M = Zr, Hf; Cp* = pentamethylcyclopentadiene), [1b, c, e] [Cp* 2 ScR], [1f] and [(neopentyl) 3 Ta = C(H)(tBu)], [1h] also activated ammonia to generate amido and nitrido complexes. There have, thus far, been examples of bimetallic oxidative addition to ammonia. A trinuclear carbonyl cluster, [Os 3 (CO) 11 (L)] (L = c-C 6 H 8 or CH 3 CN), effectively activates ammonia with the participation of the two osmium centers to produce the m-amido complex [Os 3 (CO) 10 (m-H)(m-NH 2 )]. [1a, d] A multimetallic system may work more efficiently for bond activation than a monometallic complex owing to the cooperative action of the metal centers. Each metal center would be allotted a part as a binding site and an activation site, and the transition state of the bond-activation step may, therefore, be stabilized.

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Rhodium pincer complexes of 2,2′-bis(diphenylphosphino)diphenylamine

Cited by 85 publications

References 26 publications

Square planar diphosphinoazine rhodium(I) amido carbonyl complexes with an unsymmetrical PNP′ pincer-type coordination

Square planar diphosphinoazine rhodium(I) amido carbonyl complexes with an unsymmetrical PNP′ pincer-type coordination

Gallium and indium compounds supported by a [PNP] pincer ligand

Cleavage of Nitrogen–Hydrogen Bonds of Ammonia Induced by Triruthenium Polyhydrido Clusters

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