Primary and Secondary Phosphine Complexes of Iron Porphyrins and Ruthenium Phthalocyanine: Synthesis, Structure, and P−H Bond Functionalization

Huang, Jie‐Sheng; Yu, Guang‐Ao; Xie, Jin; Wong, Kwok-Ming; Zhu, Nianyong; Che, Chi‐Ming

doi:10.1021/ic800484k

Cited by 19 publications

(8 citation statements)

References 62 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The latter mechanism appeared to be possible on the basis of the observation of previously reported alkynyl complexes (N 3 N)ZrCCPh ( 13 ) or (N 3 N)ZrCCBu via 1 H NMR spectroscopy during the catalytic reactions . This potential of direct addition was further implied by reports of hydrophosphination catalysis where the metal did not participate in the P−C bond-forming step . Interestingly, heterofunctionalization catalysts that do not directly involve the metal center in key bond-forming steps have been described for other systems …”

Section: Resultsmentioning

confidence: 94%

Insertion Reactions and Catalytic Hydrophosphination by Triamidoamine-Supported Zirconium Complexes

et al. 2010

View full text Add to dashboard Cite

Triamidoamine-supported zirconium phosphido complexes, (N 3 N)ZrPRR 0 (N 3 N=N(CH 2 CH 2 -NSiMe 3 ) 3 3-; R = alkyl, aryl; R 0 = R, H), have been shown to catalyze the hydrophosphination of terminal alkynes as well as that of symmetric aryl and alkyl carbodiimides. A mechanism based on insertion of the substrate into the Zr-P bond is proposed on the basis of competition experiments and model examples of stoichiometric insertion reactions of polar, small-molecule substrates possessing CdO, CdN, CtN, and CdS functionalities into the Zr-P bond. Molecular structures of the insertion products (N 3 N)ZrNdC(PHCy)Ph (4), (N 3 N)ZrNdC(PPh 2 )Ph (5), and (N 3 N)ZrPhNC-(O)PPh 2 (11), as well as (N 3 N)Zr[η 2 (N,N)-( i PrN) 2 C(PPh 2 )] (9), a key intermediate in the catalytic hydrophosphination of carbodiimides, have been determined.

show abstract

Section: Resultsmentioning

confidence: 94%

Insertion Reactions and Catalytic Hydrophosphination by Triamidoamine-Supported Zirconium Complexes

et al. 2010

View full text Add to dashboard Cite

show abstract

“…Primary phosphines H 2 PR are useful precursors in the synthesis of phosphorous compounds, and there is great interest in metal-mediated reactions of primary phosphines. , Similar to secondary and tertiary phosphines, primary phosphines can coordinate to metal to form phosphine complexes. However, primary phosphines are sterically less demanding as compared to their secondary and tertiary congeners and thus can more readily form metal complexes with coordination saturation. − The P–H bonds of primary phosphines can be activated by metal species to form phosphido and phosphinidene metal complexes that commonly exist in bi- and multinuclear forms with the phosphorous ligands behaving as bridging ligands. − The bridging nature renders further transformation of the phosphorous ligands difficult. Probably related to these factors, while a series of metal-catalyzed transformations of primary phosphines have been developed, − for example hydrophosphination of alkenes and alkynes ,− and phosphine dehydrocoupling; ,,− these known catalytic systems generally suffer from low catalytic efficiency.…”

Section: Introductionmentioning

confidence: 99%

Reactions of Low-Coordinate Cobalt(0)–N-Heterocyclic Carbene Complexes with Primary Aryl Phosphines

et al. 2018

View full text Add to dashboard Cite

Aiming to get knowledge on the reactivity of low-coordinate cobalt(0) species toward primary phosphines, the reactions of [(IPr)Co(vtms)2] and [(ICy)2Co(vtms)] (IPr = 1,3-bis(2′,6′-diisopropylphenyl)imidazol-2-ylidene, ICy = 1,3-dicyclohexylimidazol-2-ylidene, and vtms = vinyltrimethylsilane) with several primary aryl phosphines have been examined. The reactions of [(IPr)Co(vtms)2] and [(ICy)2Co(vtms)] with H2PDmp (Dmp = 2,6-dimesitylphenyl) at 80 °C furnish the diamagnetic cobalt(I) phosphido complexes [(NHC)Co(PHDmp)] (NHC = IPr, 1; ICy, 2) that feature the Co–(η6-mesityl) interaction. Complex 1 can coordinate CO to generate the terminal phosphido complex [(IPr)Co(CO)3(PHDmp)] (3) and can be oxidized by [Cp2Fe][BArF 4] to yield the cobalt(II) phosphido complex [(IPr)Co(PHDmp)][BArF 4] (4, BArF 4 = tetrakis(3,5-di(trifluoromethyl)phenyl)borate). For the reactions with sterically less-hindered primary phosphines, [(IPr)Co(vtms)2] is inert toward H2PC6H2-2,4,6-Me3 (H2PMes) at room temperature, whereas [(ICy)2Co(vtms)] can react with H2PMes at room temperature to produce the cobalt(II) phosphido alkyl complex trans-[(ICy)2Co(CH2CH2SiMe3)(PHMes)] (5). At 80 °C, the cobalt(0) alkene complexes [(IPr)Co(vtms)2] and [(ICy)2Co(vtms)] and also the cobalt phosphido complexes, 1, 2, and 5 can serve as precatalysts for the dehydrocoupling reaction of H2PMes to afford MesHPPHMes. NHC–Co(I)-phosphido species are proposed as the in-cycle intermediates for these cobalt-catalyzed dehydrocoupling reactions.

show abstract

“…6 Ru(II) porphyrin and phthalocyanine complexes with primary and secondary phosphines were reported for phosphine functionalization and phosphinidene transfer reactions. 7,8 Likewise, Rh(III) porphyrins have been studied in metallo radical chemistry 9 and in olefin hydrofunctionalisation, 10 although these complexes are far less commonly studied. More exotic ligands such as charged phosphoranido ligands on Rh(III) porphyrins have also been reported.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium(ii) and rhodium(iii) porphyrin phosphine complexes: influence of substitution pattern on structure and electronic properties

2011

View full text Add to dashboard Cite

Primary and Secondary Phosphine Complexes of Iron Porphyrins and Ruthenium Phthalocyanine: Synthesis, Structure, and P−H Bond Functionalization

Cited by 19 publications

References 62 publications

Insertion Reactions and Catalytic Hydrophosphination by Triamidoamine-Supported Zirconium Complexes

Insertion Reactions and Catalytic Hydrophosphination by Triamidoamine-Supported Zirconium Complexes

Reactions of Low-Coordinate Cobalt(0)–N-Heterocyclic Carbene Complexes with Primary Aryl Phosphines

Ruthenium(ii) and rhodium(iii) porphyrin phosphine complexes: influence of substitution pattern on structure and electronic properties

Contact Info

Product

Resources

About