Competitive Addition and Cycloaddition of Low Coordinated Organophosphorus Compounds To Alkoxy- and Aminoalkynes.

Lukashev, N. V.; Averin, Alexei D.; Zhichkin, Pavel; Kazankova, M. A.; Beletskaya, I. P.

doi:10.1080/10426509608545227

Cited by 14 publications

(2 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Iminophosphoranes are a good model for this behavior because the imine group can provide steric bulk in the immediate vicinity of the metal center. In contrast to α-diimines, which have been widely used as ligands for homogeneous catalysis, , diiminodiphosphorane analogues containing a P–P bond have not been readily accessible, and only a few have been reported. , Several cyclic diiminodiphosphoranes have been prepared from iminophosphanes of the type RPNMes* (R = Me, t Bu, Ph; Mes* = 2,4,6- t Bu 3 C 6 H 2 ) via P–P coupling reactions, but they exhibit trans imino substituents and are not suitable for metal chelation. There is a single example of direct diiminodiphosphorane synthesis from acyclic diphosphanes (R 2 P–PR 2 , R = Me, Et, n -Pr, n -Bu) via treatment with an inorganic azide (Me 3 SiN 3 ) .…”

Section: Introductionmentioning

confidence: 99%

Functionalization Reactions Characteristic of a Robust Bicyclic Diphosphane Framework

et al. 2013

View full text Add to dashboard Cite

The 3,4,8,9-tetramethyl-1,6-diphospha-bicyclo-[4.4.0]deca-3,8-diene (P2(C6H10)2) framework containing a P-P bond has allowed for an unprecedented selectivity toward functionalization of a single phosphorus lone pair with reference to acyclic diphosphane molecules. Functionalization at the second phosphorus atom was found to proceed at a significantly slower rate, thus opening the pathway for obtaining mixed functional groups for a pair of P-P bonded λ(5)-phosphorus atoms. Reactivity with the chalcogen-atom donors MesCNO (Mes = 2,4,6-C6H2Me3) and SSbPh3 has allowed for the selective synthesis of the diphosphane chalcogenides OP2(C6H10)2 (87%), O2P2(C6H10)2 (94%), SP2(C6H10)2 (56%), and S2P2(C6H10)2 (87%). Computational studies indicate that the oxygen-atom transfer reactions involve penta-coordinated phosphorus intermediates that have four-membered {PONC} cycles. The P-E bond dissociation enthalpies in EP2(C6H10)2 were measured via calorimetric studies to be 134.7 ± 2.1 kcal/mol for P-O, and 93 ± 3 kcal/mol for P-S, respectively, in good agreement with the computed values. Additional reactivity with breaking of the P-P bond and formation of diphosphinate O3P2(C6H10)2 was only observed to occur upon heating of dimethylsulfoxide solutions of the precursor. Reactivity of diphosphane P2(C6H10)2 with azides allowed the isolation of monoiminophosphoranes (RN)P2(C6H10)2(R = Mes, CPh3, SiMe3), and treatment with additional MesN3 yielded symmetric and unsymmetric diiminodiphosphoranes (RN)(MesN)P2(C6H10)2 (91% for R = Mes). Metalation reactions with the bulky diiminodiphosphorane ligand (MesN)2P2(C6H10)2 (nppn) allowed for the isolation and characterization of (nppn)Mo(η(3)-C3H5)Cl(CO)2 (91%), (nppn)NiCl2 (76%), and [(nppn)Ni(η(3)-2-C3H4Me)][OTf] showing that these ligands provide an attractive preorganized binding pocket for both late and early transition metals.

show abstract

Section: Introductionmentioning

confidence: 99%

Functionalization Reactions Characteristic of a Robust Bicyclic Diphosphane Framework

et al. 2013

View full text Add to dashboard Cite

show abstract

“…13 The chemistry of low-coordinate phosphorus derivatives is another interesting area in the chemistry of organophosphorus compounds. [14][15][16][17][18][19] For example, two-coordinate phosphorus derivatives with a P=N bond react with alkynes to give various hitherto-unknown compounds, such as phosphirenes, azaphosphetines and azaphosphabutadienes, depending on the substituents (Scheme 3). 20,21 Catalytic substitution producing a C sp 2-P bond Catalytic reactions with the formation of a C sp2 -P bond proved to be quite efficient in syntheses of aryl and vinyl derivatives of tetracoordinate phosphorus, which were difficult to access before.…”

mentioning

confidence: 99%