E. I. Matrosov

Complexation of (N, N-diethylthiocarbamoylmethyl) diphenylphosphine sulfide with silver nitrate. The structure of the [Ag{Ph2P(S)CH2C(S)NEt2}2]NO3 complex

Abstract(N, N-Diethylthiocarbamoylmethyl)diphenylphosphine sulfide, Ph2P(S)CH2C(S)NEt2, forms a distorted tetragonal bisligand complex [AgL2]NO3 with Ag+. The stability constant of the complex in acetonitrile was estimated by spectrophotometry (logK=3.7).

Synthesis and properties of some ethylenediphosphoryl compounds

1. n nWe synthesized some ethylenediphosphoryl compounds that contain phosphine oxide, phosphonic, and phosphinic groups. The basicity constants of the obtained esters and oxides were determined, and also the dissociation constants of the acids. n n n n n2. n nA study of the complexing properties of the acids disclosed that they form weakly stable complexes with the cations of the alkaline-earth and transition metals.

Complexation of (carbamoylmethyl)diphenylphosphine sulfide with silver nitrate. The structure of the polymeric complex [Ag2{Ph2P(S)CH2C(O)NH2}2(NO3)2] n

The reaction of (carbamoylmethyl)diphenylphosphine sulfide with AgNO3 yields the polymeric complex [Ag2{Ph2P(S)CH2C(O)NH2}2(NO3)2]n. Its structure was established by X-ray diffraction analysis. The coordination environments about both Ag+ cations are formed by five donor atoms, two of which are bonded to the metal atom substantially more weakly than the remaining three atoms. The compositions of the coordination polyhedra are different: ({AgSO′(C)O(N)O2(N′)} and {AgS′ SO(C)O2(N)}). The coordinated ligands differ in their functions: one ligand chelates the metal cation and its sulfur atom is additionally bonded to the second cation, while the second ligand acts as a bridge between the two different cations. The structure of the complex and the character of the interaction between the ligand and AgNO3 are substantially affected by the network of hydrogen bonds.

P,S-Ligands. Complexes ofP,P,P′,P′-tetraphenylethylenediphosphine monosulfide with PdCl2

Abstract1:1 and 1:2 complexes of Ph2P(CH2)2P(S)Ph2 with PdCl2 were synthesized. Their structures were established by31P NMR and IR spectroscopy and X-ray diffraction analysis. In the crystals, the 1:1 complex has a chelate structure. In CH2Cl2, this complex partially dissociates at the Pdxad.S=P bond. According to the X-ray diffraction data, only the PIII atoms the cationic chelate complex [Pd(Ph2P(CH2)2P(S)Ph2)2]2+ 2NO3−.

Complexes of (ω-diphenylphosphinoalkyl)diphenylphosphine sulfides with silver nitrate in pyridine

The behavior of the phosphine-phosphine sulfide complexes of silver, [Ph2P(S)(CH2)nPPh2]m·AgNO3 (n=2 or 4;m=1 or 2), in pyridine was studied. Dissolution of the 1:1 complexes in pyridine leads to destruction of their dimeric structures Ag2[Ph2P(S)(CH2)nPPh2]2(NO3)2 (A) to form the complexes Agpy+−P(Ph2)(CH2)nPh2P=S and Agpy+−S=PPh2(CH2)nPPh2. The solid complexes isolated from pyridine restore dimeric structure A. According to the data of X-ray diffraction analysis, the 1:2 complex isolated from pyridine has the structure [S=P(Ph2)(CH2)2(Ph2)P−(NO3)Ag(Py)−P(Ph2) (CH2)2(Ph2)P=S]Py. According to the data of IR spectroscopy, dissolution of this complex in chloroform leads to the formation of the dimeric structure Ag2Ph2P(S)(CH2)2PPh2]4(NO3)2.

The complexation of (N,N-diethylcarbamoylmethyl)diphenylphosphine sulfide with silver nitrate

The crystalline complex [Ag(L1)NO3]2 (A) was isolated by the interaction of (N,N-diethylcaibamoylmethyl)diphenylphosphine sulfide Ph2P(S)CH2C(O)NEt2 (L1) with AgNO3 in different solvents at the ratios of metal:ligand = 1∶1 and 1∶2. According to the X-ray data, complexA is a center-symmetric dimer with bridge sulfur atoms. The cations of the metal are in a tetrahedral environment formed by two S atoms and the O atoms of CO and NO3 groups. The interaction ofL1 with AgNO3 was studied in solution by IR spectroscopy, and the structures of the complexes formed are discussed.

Complexes of imidophosphoric compounds with BF3

IR,31P NMR and19F NMR spectroscopy was used to study triphenylphosphinimines with substituants at the nitrogen atom and their complexes with boron trifluoride. In the case of aryl or benzyl substituants, BF3 adds to the nitrogen atom, while the state of the phosphorus atom is close to phosphonium. An analogous structure of the intermediate complexes is proposed upon the catalysis of the imide-amide rearrangement by BF3. The introduction of acyl groups such as phosphoryl, thiophosphoryl, and methanesulfonyl groups to the nitrogen atom of the triphenylphosphinimine alters the site of attachment of BF3, which is found at the oxygen atoms of the P-O or SO2 groups or to the sulfur atom of the P-S group.

Polyphosphorus ligands, containing P(III) and P(V) in the molecule, and their complexes with palladium

ConclusionsNew polyphosphorus compounds are synthesized which contain atoms of P(III) and P(V): tetraphenylethylenediphosphine monoxide, phenylbis(β-diphenylphosphorylethyl)phosphine, and phenylbis(β-diphenylphosphinoethyl)phosphine oxide. Their acid-base properties and their complex formation with Pd(II) were studied.

Phosphine oxides and phosphorous acids containing several>P(O)CH2 groups in the molecule

1. n nThe synthesis of polymethylenepolyphosphine compounds was accomplished by the condensation of the esters of trivalent phosphorus acids with the oxides of tertiary bis- and tris(chloromethyl)phosphines and the esters of bis(chloromethyl)phosphinic acid. n n n n n2. n nThe metalation of pentaphenyldimethylenetriphosphine trioxide gave the potassium derivatives, the anions of which have a mesomeric structure, with a distribution of the charge between the oxygen and carbon atoms of the methine groups. n n n n n3. n nPhenyldistyrylphosphine oxide and diphenylphosphinic acid are formed when the dipotassium derivative of pentaphenyldimethylenetriphosphine trioxide is reacted with benzaldehyde.

Protonation of triethyl (2-pyridylimido)phosphates

Protonation of triethyl (2-pyridylimido)phosphates has been studied by potentiometric titration in nitromethane, IR and NMR spectroscopy, and X-ray structure analysis. The substances studied are protonated in one step at the N-atom of the pyridine ring. The protonated cations may be represented, according to the X-ray data, as a resonance of two structures: pyridinium and pyridoniminium; the contribution of the latter probably being considerable. Changes in spectral parameters of POEt groups upon protonation of pyridylimidophosphates (PIP) have been noted.