The rearrangement of phosphitohydrazide ligand [(ArO)2P–NPh–NPh–] into iminophosphoranate anion [(PhNP(OAr)2–NPh–] {(ArO)2P = [CH2(tBuMeC6H2O)2P]} in coordination sphere of divalent cobalt

Belina, Natalia V.; Kornev, A. N.; Sushev, Vyacheslav V.; Fukin, Georgy K.; Баранов, Е. В.; Abakumov, G. A.

doi:10.1016/j.jorganchem.2009.11.006

Cited by 9 publications

(7 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Related N to C and C to N phosphoryl transfers have been observed recently. Phosphoryl migrations were also observed in several aminophosphine systems, showing, e.g., P−N−N to NP−N rearrangements and reversible P−N−P to NP−P tautomerisms triggered by protonation/deprotonation of N , N -bisdiphenylphosphino-pyridin-2-amine . N to N phosphoryl migrations were also reported, with one example concerning the Ni(II)-induced formation of a thiazoline-diphosphine sharing analogies with 2 and 2 ′ (see Scheme ) .…”

Section: Introductionmentioning

confidence: 93%

Unexpected Metal-Induced Isomerisms and Phosphoryl Migrations in Pt(II) and Pd(II) Complexes of the Functional Phosphine 2-(Bis(diphenylphosphino)methyl)-oxazoline

2011

View full text Add to dashboard Cite

The reaction of the functional diphosphine 1 [1 = 2-(bis(diphenylphosphino)methyl-oxazoline] with [PtCl(2)(NCPh)(2)] or [PdCl(2)(NCPh)(2)], in the presence of excess NEt(3), affords [Pt{(Ph(2)P)(2)C···C(···NCH(2)CH(2)O)}(2)] ([Pt(1(-H)-P,P)(2)], 3a) and [Pd{(Ph(2)P)(2)C···C(···NCH(2)CH(2)O)}(2)] ([Pd(1(-H)-P,P)(2)], 3b), respectively, in which 1(-H) is (oxazoline-2-yl)bis(diphenylphosphino)methanide. The reaction of 3b with 2 equiv of [AuCl(tht)] (tht = tetrahydrothiophene) afforded [Pd(1(-H)-P,N)(2)(AuCl)(2)] (4), as a result of the opening of the four-membered metal chelate since ligand 1(-H), which was P,P-chelating in 3b, behaves as a P,N-chelate toward the Pd(II) center in 4 and coordinates to Au(I) through the other P donor. In the absence of a base, the reaction of ligand 1 with [PtCl(2)(NCPh)(2)] in MeCN or CH(2)Cl(2) afforded the isomers [Pt{(Ph(2)P)(2)C═C(OCH(2)CH(2)NH)}(2)]Cl(2) ([Pt(1'-P,P)(2)]Cl(2) (5), 1' = 2-(bis(diphenylphosphino)methylene)-oxazolidine) and [Pt{(Ph(2)P)(2)C═C(OCH(2)CH(2)NH)}{Ph(2)PCH═C(OCH(2)CH(2)N(PPh(2))}]Cl(2) ([Pt(1'-P,P)(2'-P,P)]Cl(2) (6), 2' = (E)-3-(diphenylphosphino)-2-((diphenylphosphino)methylene)oxazolidine]. The P,P-chelating ligands in 5 result from a tautomeric shift of the C-H proton of 1 to the nitrogen atom, whereas the formation of one of the P,P-chelates in 6 involves a carbon to nitrogen phosphoryl migration. The reaction of 5 and 6 with a base occurred by deprotonation at the nitrogen to afford 3a and [Pt{(Ph(2)P)(2)C···C(···NCH(2)CH(2)O)}{Ph(2)PCH═COCH(2)CH(2)N(PPh(2))}]Cl ([Pt(1(-H)-P,P)(2'-P,P)]Cl (7)], respectively. In CH(2)Cl(2), an isomer of 3a, [Pt{Ph(2)P)(2)C···C(···NCH(2)CH(2)O)}{Ph(2)PC(PPh(2))═COCH(2)CH(2)N}] ([Pt(1(-H)-P,P)(1(-H)-P,N)] (8)), was obtained as a side product which contains ligand 1(-H) in two different coordination modes. Complexes 3b·4CH(2)Cl(2), 4·CHCl(3), 6·2.5CH(2)Cl(2), and 8·CH(2)Cl(2) have been structurally characterized by X-ray diffraction.

show abstract

Section: Introductionmentioning

confidence: 93%

Unexpected Metal-Induced Isomerisms and Phosphoryl Migrations in Pt(II) and Pd(II) Complexes of the Functional Phosphine 2-(Bis(diphenylphosphino)methyl)-oxazoline

2011

View full text Add to dashboard Cite

show abstract

“…We have previously reported a migratory insertion of an R 2 P group into the nitrogen-nitrogen bond of a phosphinohydrazide ligand, namely, R 2 P-NR-NRf RNdPR 2 -NR-, which in general occurred in the coordination sphere of s, d, and f metals. [6][7][8][9][10] This migration is a novel and useful approach to the synthesis of phosphazenides and phosphinoamides. Here, we discuss the unique properties of the diphosphinohydrazine 1 and diphosphinohydrazide ligand bearing a quinolyl substituent.…”

Section: Introductionmentioning

confidence: 99%

Chemistry of the Phosphorus−Nitrogen Ligands. Multiple Isomeric Transformations of the Diphosphinohydrazine Bearing 8-Quinolyl Substituent: P→C, P→N, and P→P Migrations Caused by Different Factors

et al. 2010

Self Cite

View full text Add to dashboard Cite

The reaction of 8-quinolylhydrazine with 2 equiv of Ph(2)PCl in the presence of Et(3)N gives 8-[(Ph(2)P)(2)NNH]-Quin (1) (Quin = quinolyl) in 84% yield. The heating of 1 at 130 °C for 1 h in toluene results in migration of the [Ph(2)PNPPh(2)] group to a carbon atom of the quinolyl fragment to form an isomer, 7-(Ph(2)P-N═PPh(2))-8-NH(2)-Quin (2). The same migration is caused by the addition of LiN(SiMe(3))(2) to 1. On the contrary, lithiation of 1 with n-BuLi followed by the addition of ZnI(2) (1:1) affords the aminoquinolyl-phosphazenide dinuclear complex [ZnI(8-Quin-NPPh(2)═N-PPh(2))-κ(3)N,N,P](2) (4), which is a result of P→N migration. Compound 1 itself reacts with ZnI(2) in THF to form 4 and protonated molecule 1·HI, which rearranges to the more stable iminobiphosphine salt (Ph(2)P-PPh(2)═N-NH-Quin-8)·HI. Zinc iodide reacts with 2 equiv of the lithium salt of 1 without rearrangement, to form homoleptic aminoquinolyl zinc complex Zn[{(Ph(2)P)(2)NN-Quin-8}-κ(2)N,N](2) (6). Solutions of 4 and 2 in dichloromethane show luminescence at 510 and 460 nm (quantum yields are 45% and 7%, respectively). DFT calculations were provided for possible isomers and their complexes.

show abstract

“…At the same time, more sterically hindered LiN(SiMe 3 ) 2 does not react with 1 at all. Thus, the behavior of 1 , containing a bulky t Bu group, in metalation reactions is quite different from that of known phosphinohydrazines. − …”

Section: Resultsmentioning

confidence: 98%

“…Interestingly, the lithium salt of 1 was not obtained at ambient conditions while many other lithium phosphinohydrazides were characterized in crystalline form or in solution. − Thus, unexpectedly the reaction between 1 and MeLi in toluene/Et 2 O solution gave a mixture of products, LiPPh 2 , Ph 2 P–PPh 2 , Ph 2 PMe and t Bu–PPh 2 according to the 31 P NMR spectra and chromatography–mass spectrometry measurements (Supporting Information, page 8). Interaction of 1 with n -BuLi proceeds in a similar way to give Ph 4 P 2 and LiPPh 2 as the main products.…”

Section: Resultsmentioning

confidence: 99%

“…As an example, it is known that the triphosphazenide ligand [Ph 2 P–NPPh 2 –NPPh 2 ] − may be synthesized only in the coordination sphere of transition metals by the disproportionation of bis(diphenylphosphino)amide anion. − So, cobalt(II) chloride and LiN(PPh 2 ) 2 in boiling toluene form a triphosphazenide anion by oxidative scrambling of the amide, which reacts further with cobalt(II) to give the spirocyclic metallaphosphazene . During our study we described the rearrangement of phosphinohydrazides, − which may be considered as a useful approach to the synthesis of phosphazenides and phosphinoamides (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

The Intramolecular Rearrangement of Phosphinohydrazides [R′₂P–NR–NR–M] → [RN═PR′₂–NR–M]: General Rules and Exceptions. Transformations of Bulky Phosphinohydrazines (R–NH–N(PPh₂)₂, R =tBu, Ph₂P)

et al. 2011

Self Cite

View full text Add to dashboard Cite

Reactions of diphosphinohydrazines R-NH-N(PPh(2))(2) (R = tBu (1), Ph(2)P (3)) with some metalation reagents (Co[N(SiMe(3))(2)](2), LiN(SiMe(3))(2), La[N(SiMe(3))(2)](3), nBuLi, MeLi) were performed. Compound 1 was synthesized by the reaction of Ph(2)PCl with tert-butylhydrazine hydrochloride in 83% yield. This compound reveals temperature-dependent (31)P NMR spectra due to hindered rotation about the P-N bonds. Complicated redox reaction of 1 with Co[N(SiMe(3))(2)](2) proceeds with cleavage of the P-N and N-N bonds to form a binuclear cobalt complex [Co{HN(PPh(2))(2)-κ(2)P,P'}(2)(μ-PPh(2))](2) (2) demonstrating a short Co···Co distance of 2.3857(5) Å, which implies a formal double bond between the Co atoms. Strong nucleophiles (nBuLi, MeLi) cause fragmentation of the molecules 1 and 3, while reactions of 3 with lithium and lanthanum silylamides give products of the NNP → NPN rearrangement [Li{Ph(2)P(NPPh(2))(2)-κ(2)N,N'}(THF)(2)] (4) and [La{Ph(2)P(NPPh(2))(2)-κ(2)N,N'}{N(SiMe(3))(2)}(2)] (5), respectively. These complexes represent the first examples of a κ(2)N,N' bonding mode for the triphosphazenide ligand [(Ph(2)PN)(2)PPh(2)](-). DFT calculations showed large energy gain (52.1 kcal/mol) of the [NNP](-) to [NPN](-) anion rearrangement.

show abstract

The rearrangement of phosphitohydrazide ligand [(ArO)2P–NPh–NPh–] into iminophosphoranate anion [(PhNP(OAr)2–NPh–] {(ArO)2P = [CH2(tBuMeC6H2O)2P]} in coordination sphere of divalent cobalt

Cited by 9 publications

References 6 publications

Unexpected Metal-Induced Isomerisms and Phosphoryl Migrations in Pt(II) and Pd(II) Complexes of the Functional Phosphine 2-(Bis(diphenylphosphino)methyl)-oxazoline

Unexpected Metal-Induced Isomerisms and Phosphoryl Migrations in Pt(II) and Pd(II) Complexes of the Functional Phosphine 2-(Bis(diphenylphosphino)methyl)-oxazoline

Chemistry of the Phosphorus−Nitrogen Ligands. Multiple Isomeric Transformations of the Diphosphinohydrazine Bearing 8-Quinolyl Substituent: P→C, P→N, and P→P Migrations Caused by Different Factors

The Intramolecular Rearrangement of Phosphinohydrazides [R′₂P–NR–NR–M] → [RN═PR′₂–NR–M]: General Rules and Exceptions. Transformations of Bulky Phosphinohydrazines (R–NH–N(PPh₂)₂, R =tBu, Ph₂P)

Contact Info

Product

Resources

About

The rearrangement of phosphitohydrazide ligand [(ArO)2P–NPh–NPh–] into iminophosphoranate anion [(PhNP(OAr)2–NPh–] {(ArO)2P = [CH2(tBuMeC6H2O)2P]} in coordination sphere of divalent cobalt

Cited by 9 publications

References 6 publications

Unexpected Metal-Induced Isomerisms and Phosphoryl Migrations in Pt(II) and Pd(II) Complexes of the Functional Phosphine 2-(Bis(diphenylphosphino)methyl)-oxazoline

Unexpected Metal-Induced Isomerisms and Phosphoryl Migrations in Pt(II) and Pd(II) Complexes of the Functional Phosphine 2-(Bis(diphenylphosphino)methyl)-oxazoline

Chemistry of the Phosphorus−Nitrogen Ligands. Multiple Isomeric Transformations of the Diphosphinohydrazine Bearing 8-Quinolyl Substituent: P→C, P→N, and P→P Migrations Caused by Different Factors

The Intramolecular Rearrangement of Phosphinohydrazides [R′2P–NR–NR–M] → [RN═PR′2–NR–M]: General Rules and Exceptions. Transformations of Bulky Phosphinohydrazines (R–NH–N(PPh2)2, R =tBu, Ph2P)

Contact Info

Product

Resources

About

The Intramolecular Rearrangement of Phosphinohydrazides [R′₂P–NR–NR–M] → [RN═PR′₂–NR–M]: General Rules and Exceptions. Transformations of Bulky Phosphinohydrazines (R–NH–N(PPh₂)₂, R =tBu, Ph₂P)