Coordination chemistry of cyclamphosphorane. Access to transition-metal cyclamphosphoranides. Crystal and molecular structure of dicarbonylcyclopentadienylmolybdenum cyclamphosphoranide complex

Dupart, J. M.; Grand, André; Riess, Jean G.

doi:10.1021/ja00266a009

Cited by 28 publications

(6 citation statements)

References 7 publications

(11 reference statements)

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“…( c y c l a m~~) ] C1, a simple P(II1)---N(II1) chelate compound derived from form b of the ligand (2,3). A strong base, methyl lithium, is required to convert this initial product to [~o (~O )~(~~-C~~~) ( c~c l a with an r12-coordinated P-N bond (2,3).…”

Section: In Contrast In the Reaction Of Cyclamph With [ M O C I ( mentioning

confidence: 99%

“…A strong base, methyl lithium, is required to convert this initial product to [~o (~O )~(~~-C~~~) ( c~c l a with an r12-coordinated P-N bond (2,3). The rhodium complex, [RhCl(CO)(cyclamPH)], also contains a P(II1)---N(II1) chelated ligand (2).…”

Section: In Contrast In the Reaction Of Cyclamph With [ M O C I ( mentioning

confidence: 99%

“…The coordination chemistry of "cyclenphosphorane", I (n = 2, and "cyclamphosphorane", I (n = 3), has attracted recent attention for several reasons (1,2). Most novel are complexes in which a P-N bond of the deprotonated PV form is r12-coordinated to a metal to form a three-membered ring (1)(2)(3).…”

Section: Introductionmentioning

confidence: 99%

“…Most novel are complexes in which a P-N bond of the deprotonated PV form is r12-coordinated to a metal to form a three-membered ring (1)(2)(3). However, the relatively subtle effects of ring size on the distribution of a and b forms are also interesting.…”

Section: Introductionmentioning

confidence: 99%

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Reactions of "cyclen-" and "cyclam-phosphorane" with [Pt₂Cl₄(PEt₃)₂]. Monodentate and bidentate complexes and the crystal and molecular structure of [PtCl(PEt₃)(cyclamPH)]Cl_•CH₂Cl₂

Berry¹,

Browning²,

Bushnell³

et al. 1989

Can. J. Chem.

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Chem. 67, 48 (1989).Reaction of "cyclamphosphorane" (cyclamPH) with [Pt2C14(PEt3)2] yields [PtC1(PEt3)(cyclamPH)]C1. The complex crystallizes as a dichloromethane solvate in the monoclinic space group P2, I n , with a = 13.877(3), b = 23.231(7), c = 8.295(2) A, P = 91.86(4)", and an X-ray diffraction study shows square planar platinum coordination in which the labile proton of cyclamPH has transferred from phosphorus to nitrogen and the ligand is attached via simple P(II1)---N(II1) chelation. The phosphorus is trans to chlorine in the platinum coordination plane.The corresponding product, trans-[PtC12(PEt3)(cyclenPH2)]C1, derived from reaction of "cyclenphosphorane" (cyclenPH) with [Pt2C14(PEt3)2], is shown by NMR studies to have a quite different structure in which the ligand is protonated at two nitrogen sites but not at phosphorus. The phosphorus is pentacoordinate with four attachments to nitrogel, atoms and one to platinum. The two chlorine atoms are mutually trans in the platinum coordination plane.Key words: crystal structure, cyclenphosphorane reaction, cyclamphosphorane reaction, X-ray diffraction. Les deux atomes de chlore sont mutuellement trans dans le plan de coordination du platine.

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Section: In Contrast In the Reaction Of Cyclamph With [ M O C I ( mentioning

confidence: 99%

Section: In Contrast In the Reaction Of Cyclamph With [ M O C I ( mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Reactions of "cyclen-" and "cyclam-phosphorane" with [Pt₂Cl₄(PEt₃)₂]. Monodentate and bidentate complexes and the crystal and molecular structure of [PtCl(PEt₃)(cyclamPH)]Cl_•CH₂Cl₂

Berry¹,

Browning²,

Bushnell³

et al. 1989

Can. J. Chem.

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“…Synthesis and properties of compounds bearing a hypervalent group 15 element−transition metal bond have attracted interests recently. − However, many of the compounds obtained hitherto are unstable toward atmospheric moisture and systematic investigation of quantitative effects of the transition metal fragments on the properties of metalated hypervalent group 15 element compounds has not been carried out mainly because of the instabilty of these compounds. Among the properties of these compounds, the stereochemical rigidity of metalated pentacoordinate compounds is interesting for us because of the following observations: (i) The positional isomerization (pseudorotation) in pentacoordinate compounds is facile, especially in acyclic compounds .…”

Section: Introductionmentioning

confidence: 99%

Evidence for Intramolecular Permutation (Pseudorotation) at the Central Antimony Atom and Strong Equatophilicity of an Iron and a Ruthenium Ligand in Pentacoordinate Hypervalent Antimony Compounds

et al. 2000

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Diastereomeric pentacoordinate hypervalent stiboranes with an Sb−Fe bond {4a and 4b: RfRfm*Sb*FeCp(CO)2 {Rf = o-C6H4C(CF3)2O-, Rfm* = o-C6H4C*(CF3)(Me)O-} were synthesized by the reaction of stiboranide anion, RfRfm*Sb*-Li+ (3-Li), with CpFeI(CO)2 in the presence of AgBF4. The carbonyl group of 4 was replaced with triphenylphosphine by irradiation with a tungten lamp to give a mixture of four diastereomers {5a−5d: RfRfm*Sb*Fe*Cp(CO)(PPh3)}. Each of the diastereomers was separated by TLC, and the relative stereochemistry was determined by X-ray crystallographic analysis. The thermal equilibration from the pure diastereomer of 5 indicated that the isomerization took place through inversion (pseudorotation) at the central antimony atom. The pseudorotational barriers of 5 were much higher than those of Rf2Sb*Cl and RfRfm*Sb*(p-CH3C6H4). These results are consistent with the electron-donating properties of the group 8 transition metal fragment. Hypervalent stiboranes {6, Rf2Sb*Fe*Cp(CO)(PMe3); 7, Rf2Sb*Fe*Cp(CO)(PEt3)} were also prepared by similar procedures. The order of pseudorotational barriers [2 {Rf2Sb*Fe*Cp(CO)(PPh3)} (32.8, 33.2 kcal/mol) > 7 (32.5, 32.9 kcal/mol) > 6 (32.2, 32.7 kcal/mol)] suggests that the steric effect of the iron ligand also played a role. The pseudorotational barriers of the corresponding ruthenium compounds, RfRfm*Sb*RuCp(CO)2 (12a and 12b), were slightly higher than those of the corresponding iron compounds (4a and 4b).

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Grafting of Tetraazamacrocycles on the Surface of Phosphorus-Containing Dendrimers

et al. 1999

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Three types of tetraazamacrocycles (1,4,8,11‐tetraazacyclotetradecane, 1,4,8,12‐tetraazacyclopentadecane, and 1,4,8,11‐tetraazacyclotetradecane‐5,7‐dione) are grafted on the surface of phosphorus‐containing dendrimers possessing P(S)Cl2 end groups (for generations 1 and 3: this corresponds to three and twelve macrocycles, respectively) and on the model compound PhCHNN(Me)P(S)Cl2. Depending on the nature of the macrocycle, the reaction induces the formation of five‐membered rings (diazaphospholanes) or of six‐membered rings (diazaphosphorinanes). The structure of the adducts is deduced from 13C NMR spectra and from X‐ray diffraction studies of the reaction products (8, 9, 10) of the model compound.

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Coordination chemistry of cyclamphosphorane. Access to transition-metal cyclamphosphoranides. Crystal and molecular structure of dicarbonylcyclopentadienylmolybdenum cyclamphosphoranide complex

Cited by 28 publications

References 7 publications

Reactions of "cyclen-" and "cyclam-phosphorane" with [Pt₂Cl₄(PEt₃)₂]. Monodentate and bidentate complexes and the crystal and molecular structure of [PtCl(PEt₃)(cyclamPH)]Cl_•CH₂Cl₂

Reactions of "cyclen-" and "cyclam-phosphorane" with [Pt₂Cl₄(PEt₃)₂]. Monodentate and bidentate complexes and the crystal and molecular structure of [PtCl(PEt₃)(cyclamPH)]Cl_•CH₂Cl₂

Evidence for Intramolecular Permutation (Pseudorotation) at the Central Antimony Atom and Strong Equatophilicity of an Iron and a Ruthenium Ligand in Pentacoordinate Hypervalent Antimony Compounds

Grafting of Tetraazamacrocycles on the Surface of Phosphorus-Containing Dendrimers

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Coordination chemistry of cyclamphosphorane. Access to transition-metal cyclamphosphoranides. Crystal and molecular structure of dicarbonylcyclopentadienylmolybdenum cyclamphosphoranide complex

Cited by 28 publications

References 7 publications

Reactions of "cyclen-" and "cyclam-phosphorane" with [Pt2Cl4(PEt3)2]. Monodentate and bidentate complexes and the crystal and molecular structure of [PtCl(PEt3)(cyclamPH)]Cl•CH2Cl2

Reactions of "cyclen-" and "cyclam-phosphorane" with [Pt2Cl4(PEt3)2]. Monodentate and bidentate complexes and the crystal and molecular structure of [PtCl(PEt3)(cyclamPH)]Cl•CH2Cl2

Evidence for Intramolecular Permutation (Pseudorotation) at the Central Antimony Atom and Strong Equatophilicity of an Iron and a Ruthenium Ligand in Pentacoordinate Hypervalent Antimony Compounds

Grafting of Tetraazamacrocycles on the Surface of Phosphorus-Containing Dendrimers

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Reactions of "cyclen-" and "cyclam-phosphorane" with [Pt₂Cl₄(PEt₃)₂]. Monodentate and bidentate complexes and the crystal and molecular structure of [PtCl(PEt₃)(cyclamPH)]Cl_•CH₂Cl₂

Reactions of "cyclen-" and "cyclam-phosphorane" with [Pt₂Cl₄(PEt₃)₂]. Monodentate and bidentate complexes and the crystal and molecular structure of [PtCl(PEt₃)(cyclamPH)]Cl_•CH₂Cl₂