Metal(II) methylphenylphosphinates

Mikulski, Chester M.; Unruh, Joseph; DELACATO, D.; Iaconianni, Frank J.; Pytlewski, L.L.; Karayannis, Nicholas M.

doi:10.1016/0022-1902(81)80377-6

Cited by 10 publications

(5 citation statements)

References 43 publications

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“…Although organophosphinates of manganese(I1) have been reported in the literature (8,9,(21)(22)(23)(24)(25)(26)(27), no detailed X-ray crystallographic or cryomagnetic studies on these compounds have been previously undertaken. We found that slow crystallization of the dimethylphosphinate derivative from dilute solution gave well-formed pale pink crystals which, according to elemental analysis and infrared studies, incorporate two molecules of water per manganese.…”

Section: Resultsmentioning

confidence: 99%

Magnetic properties of anhydrous and hydrated dimethylphosphinates of manganese(II). The crystal and molecular structure of poly-bis(μ-dimethylphosphinato)diaquomanganese(II)

Cicha¹,

Haynes²,

Oliver³

et al. 1985

Can. J. Chem.

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Can. J. Chem. 63, 1055 (1985. The dimethylphosphinate of manganese(ll), Mn[(CH3)zP02]2, and its dihydrate have been prepared and studied using magnetic susceptibility, differential scanning calorimetry, and electronic and vibrational spectroscopic methods. The dihydrate was obtained in crystalline form and a single crystal X-ray diffraction study revealed a polymeric structure.Crystals of~poly-bis(p-dimethylphosphinato)diaquomanganese(l1) are monoclinic, o = 20.722(3), b = 4.8652(2), c = 11.0689(14) A, P = 102.209(7)", Z = 4, space group C2/c. The structure was solved by conventional heavy-atom methods and was refined by full-matrix least-squares procedures to R = 0.030 and R,,. = 0.033 for 983 reflections with I 2 3u(I). The structure consists of infinite centrosymmetric chains of Mn(ll) atoms linked by double phosphinate bridges and extending along the crystallographic b axis. The water molecu!es are involved in both interchain and bifurcated intrachain hydrogen bonding (0.--0 = 2.734(2), 2.899(3) and 3.120(3) A). The coordination about Mn is slightly distorteG octahedral with librationcorrected bond lengths Mn-O(phosphinato) = 2.156(2) and 2.212(2), Mn-OH2 = 2.247(2) A. Magnetic susceptibility studies on the dihydrate from 300 to 4.2 K reveal a magnetic moment of -5.9 BM over most of the range and give no evidence for significant magnetic exchange. The anhydrous compound, which is considered on the basis of indirect evidence to retain the double phosphinate bridged structure exhibited by the dihydrate, shows relatively strong antiferromagnetic behaviour. The data have been analyzed according to two theoretical models both of which employ the isotropic Heinsenberg Hamiltonian. The scaling model of Wagner and Friedberg gives J = -2.94 cm-' and g = 2.02 and the interpolation scheme of Weng gives J = -2.69 cm-' and g = 2.01. The magnitude of the exchange coupling is considered in relation to that observed in related manganese compounds and possible reasons for the observed damping of the exchange on hydration are discussed. Les etudes de susceptibiliti magnttique, rCalisCes avec I'hydrate double ii des temperatures allant de 300 a 4,2 K, rtvklent la presence d'un moment magnttique de 5.9 BM environ sur presque tout I'intervalle considtrk. Le compose anhydre, qui, d'aprts des preuves indirectes, conserverait la structure pontCe double phosphinate qui existe dans le dihydrate, exhibe un comportement antiferromagnktique relativement fort. On a analysC les donntes selon deux modtles thkoriques qui utilisent I'Hamiltonien isotrope de Heinsenberg. Le modble proportionnt de Wagner et Friedberg permet de prtdire des valeurs de J = -2,94 cm-' et g = 2,02 alors que le schema d'interpolation de Weng conduit a des valeurs de J = -2,69 cm-' et g = 2,01. On considkre I'amplitude du couplage d'echange en rapport avec celui observe avec des composes apparentes du mangankse et on discute des raisons qui pourraient expliquer le fait que I'tchange accompagnant I'hydratation est amoindri.[Traduit par le journal] Introduction The po...

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Section: Resultsmentioning

confidence: 99%

Magnetic properties of anhydrous and hydrated dimethylphosphinates of manganese(II). The crystal and molecular structure of poly-bis(μ-dimethylphosphinato)diaquomanganese(II)

Cicha¹,

Haynes²,

Oliver³

et al. 1985

Can. J. Chem.

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“…19 Calcium methylphenylphosphinates were soluble in water and methanol and precipitated as dihydrates; the anhydrous complexes could be isolated at 100 °C in vacuo. 20 Singly and doubly deprotonated P,P′diphenylmethylenediphosphinic acid H 2 C[P(Ph)(O)OH] 2 forms polymeric structures with magnesium and calcium ions. 21 The oxidation of diphenylphosphanide with the homologous chalcogens leads to thio-and selenophosphinites and -phosphinates.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The phosphinates of the heavier alkaline earth metals were studied by IR spectroscopy to investigate the symmetry of the O–P–O moiety . Calcium methylphenylphosphinates were soluble in water and methanol and precipitated as dihydrates; the anhydrous complexes could be isolated at 100 °C in vacuo . Singly and doubly deprotonated P,P ′-diphenylmethylenediphosphinic acid H 2 C[P(Ph)(O)OH] 2 forms polymeric structures with magnesium and calcium ions …”

Section: Introductionmentioning

confidence: 99%

Oxidation Products of Calcium and Strontium Bis(diphenylphosphanide)

et al. 2012

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The tetrahydrofuran adducts [(thf)(4)M(PPh(2))(2)] (M = Ca, Sr) are air sensitive and can easily be oxidized by chalcogens. Metalation of diphenylphosphane oxide, diphenylphosphinic acid, and diphenyldithiophosphinic acid as well as salt metathetical approaches of the potassium salts with MI(2) allow the synthesis of [(thf)(4)Ca(OPPh(2))(2)] (1), [(dmso)(2)Ca(O(2)PPh(2))(2)] (2), [(thf)(3)Ca(O(2)PPh(2))I](2) (3), [(thf)(3)Ca(S(2)PPh(2))(2)] (4), [(thf)(2)Ca(Se(2)PPh(2))(2)] (5), [(thf)(3)Sr(S(2)PPh(2))(2)] (6), [(thf)(3)Sr(Se(2)PPh(2))(2)] (7), and [(thf)(2)Ca(O(2)PPh(2))(S(2)PPh(2))](2) (8), respectively. The diphenylphosphinite anion in 1 contains a phosphorus atom in a trigonal pyramidal environment and binds terminally via the oxygen atom to calcium. The diphenylphosphinate anions act as bridging ligands leading to polymeric structures of calcium bis(diphenylphosphinates). Therefore strong Lewis bases such as dimethylsulfoxide (dmso) are required to recrystallize this complex yielding chain-like 2. The chain structure can also be cut into smaller units by ligands which avoid bridging positions such as iodide and diphenyldithiophosphinate (3 and 8, respectively). In general, diphenyldithio- and -diselenophosphinate anions act as terminal ligands and allow the isolation of mononuclear complexes 4 to 7. In these molecules the alkaline earth metals show coordination numbers of six (5) and seven (4, 6, and 7).

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“…A very tentative interpretation of this effect is that the neutralizing agents react with residual HCI, adsorbed on the polymer surface, to form CaC12 and ZnCl2, which in turn undergo reactions of type (1) with DMMP or TMP. In fact, the phosphoryl methyl esters would not be likely to drive off any residual HCl, but they would be expected to react with any metal chloride, yielding the corresponding methyl methylphosphonato or dimethylphosphato metal complex and CH3Cl.1-5J5, 24 The tendency of CaC12 or ZnClz to undergo reactions of type (1) with phosphoryl methyl esters has been recently demonstrated in a study of reactions of methyl methylphenylphosphinate with various MC12 salts (M = Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, Cd, Sn), which invariably led to the precipitation of the corresponding bis( methylphenylphosphinato) metal(I1) complexes.24 Table I1 shows corrosivity data for bulk polypropylene pellets prepared by extrusion in the presence or absence of neutral phosphoryl methyl esters. These results clearly indicate that inclusion of the phosphoryl esters in the stabilizer package results in noncorrosive polymer pellets.…”

Section: Resultsmentioning

confidence: 99%

Neutral organophosphoryl methyl ester–metal chloride interactions as applied to the dechlorination of catalyst residues in polypropylenes prepared by solventless processes

Karayannis¹,

Khelghatian²,

Skryantz³

1982

J of Applied Polymer Sci

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SynopsisA novel method of dechlorinating catalyst residues in polypropylenes prepared by solventless processes is reported. The method is based on the reaction of the metal chlorides present in these residues with neutral organophosphoryl methyl esters, such as trimethyl phosphate and dimethyl methylphosphonate. These reactions lead to the formation of, complexes, with evolution of the chloride in the form of methyl chloride. Experimental evidence presented demonstrates that inclusion of one of the preceding esters in the stabilizer package of polypropylene powders prepared by the hulk polymerization process and containing 300-650 ppm C1, followed by extrusion and pelletization, can result in practically complete dechlorination (C1 content less than 5 ppm) of the polymer.

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Metal(II) methylphenylphosphinates

Cited by 10 publications

References 43 publications

Magnetic properties of anhydrous and hydrated dimethylphosphinates of manganese(II). The crystal and molecular structure of poly-bis(μ-dimethylphosphinato)diaquomanganese(II)

Magnetic properties of anhydrous and hydrated dimethylphosphinates of manganese(II). The crystal and molecular structure of poly-bis(μ-dimethylphosphinato)diaquomanganese(II)

Oxidation Products of Calcium and Strontium Bis(diphenylphosphanide)

Neutral organophosphoryl methyl ester–metal chloride interactions as applied to the dechlorination of catalyst residues in polypropylenes prepared by solventless processes

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