Linear alkaline earth metal phosphinate coordination polymers: synthesis and structural characterization

Rood, Jeffrey A.; Huttenstine, Ashley L.; Schmidt, Zachery A.; White, Michael R. H.; Oliver, Allen G.

doi:10.1107/s2052520614004247

Cited by 7 publications

(4 citation statements)

References 35 publications

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“…Dialkylphosphinates have also been used to obtain high loadings of metals into polymers to increase flame retardancy [13]. It is also possible to form metal organic frameworks (MOFs) from polyphosphinic acids [14,15]. Their ability to form stable complexes in solution, particularly with borderline or hard metal cations, is exploited in extractive hydrometallurgy using solvent extraction to achieve the concentration and separation of particular metals [16,17].…”

Section: Introductionmentioning

confidence: 99%

Metal-binding motifs of alkyl and aryl phosphinates; versatile mono and polynucleating ligands

Carson¹,

Healy²,

Doidge³

et al. 2017

Coordination Chemistry Reviews

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An analysis of 552 structures of metal complexes of alkyl and arylphosphinates in the Cambridge Crystallographic Database shows that the phosphinate ligating group is remarkably versatile and is able to adopt ten different binding motifs in both mono-and polynuclear complexes in which an individual phosphinate group can bind to up to five metal atoms. The majority of both homo-and heteroleptic complexes contain M-O-PR2-O-M units in oligomeric and polymeric structures. In many heteroleptic complexes ligands containing hydrogen bond donors form strong bonding interactions with the phosphinate, generating pseudochelated structures. Similar pseudochelates, − O-PR2=O … H-O-PR2=O, are formed when both a phosphinate and its parent phosphinic acid are coordinated to a single metal atom. Such structures feature also in the solution chemistry involved in metal extraction processes using phosphinate ligands. As might be expected, many of the binding motifs found in phosphinate complexes are similar to those in carboxylate complexes but there are fewer examples of phosphinates being used to form metal organic frameworks.

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Section: Introductionmentioning

confidence: 99%

Metal-binding motifs of alkyl and aryl phosphinates; versatile mono and polynucleating ligands

Carson¹,

Healy²,

Doidge³

et al. 2017

Coordination Chemistry Reviews

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“… 1 These compounds are only sparingly soluble in common organic solvents and form coordination polymers in the solid state; strong bases such as DMF and DMSO are required to crystallize strand structures with bridging diphenylphosphinato ligands. 2 , 3 In the heteroleptic thf adduct of Ph 2 P(O)O–Ca–X (X = Br, I), 2 , 4 the phosphinato anion shows a bridging coordination mode. 4 In homologous dithiophosphinates, the Ph 2 P(S)S – ligands act as bidentate Lewis bases at one metal atom, allowing the isolation of highly soluble discrete molecular complexes.…”

Section: Introductionmentioning

confidence: 99%

“…Phosphinates of group 2 metals (Ae) such as alkaline-earth metal diphenylphosphinates (L) n Ae[OP(O)Ph 2 ] 2 are well known since many decades and have been studied by IR spectroscopy already in the 1970s, verifying charge delocalization within the O–P–O moiety . These compounds are only sparingly soluble in common organic solvents and form coordination polymers in the solid state; strong bases such as DMF and DMSO are required to crystallize strand structures with bridging diphenylphosphinato ligands. , In the heteroleptic thf adduct of Ph 2 P(O)O–Ca–X (X = Br, I), , the phosphinato anion shows a bridging coordination mode . In homologous dithiophosphinates, the Ph 2 P(S)S – ligands act as bidentate Lewis bases at one metal atom, allowing the isolation of highly soluble discrete molecular complexes …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Oligonuclear Structures of Strontium and Barium Complexes with Protonated and Deprotonated N-Mesityl-P,P-diphenylphosphinic Amide Ligands

et al. 2021

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Metalation of N -mesityl- P , P -diphenylphosphinic amide Ph 2 P(O)-NHMes (HL, I ) with MgBu 2 and Ae{N(SiMe 3 ) 2 } 2 (Ae = Ca, Sr, and Ba) yields alkaline-earth metal complexes with the compositions of [(thf) n Ae(L·HL) 2 ] [Ae/n = Mg/0 ( II ), Ca/2 ( III )] as well as of [Sr 2 L 3 (L·HL)(HL)] ( 1 ), [Ba 2 L 3 (L·HL)(HL)] ( 2 ), [Ba 3 L 6 ] ( 3 ), and [(thf) 2 Ba 3 L 6 ] ( 4 ). In III , 1 , 2 , and 3 , the alkaline-earth metal atoms are in severely distorted octahedral environments, and the structural distortions are partially caused by the small O-Ae-N bite angles of the chelating Ph 2 P(O)-NMes anions. The substructures (L·HL) contain N–H···N hydrogen bridges, stabilizing the arrangement of the ligands in complexes II , III , 1 , and 2 . In the trinuclear barium complex [Ba(μ-L) 3 Ba(μ-L) 3 Ba] ( 3 ), a rigid adjustment of the anionic L bases leads to a C 3 -symmetric molecule in the crystalline state with bridging oxygen atoms. Due to the small O–Ba–N bite angles of the chelating anions, vacant coordination sites are available at the outer barium centers. Coordination of thf bases in these gaps yields the complex [(thf)Ba(μ-L) 3 Ba(μ-L) 3 Ba(thf)] ( 4 ). However, THF is unable to deaggregate the trinuclear complexes into smaller barium-containing moieties. Increasing the radius of the alkaline-earth metals and increasing the nuclearity of these compounds lead to decreasing solubility in common organic solvents. NMR studies verify that the molecular structures of these alkaline-earth metal complexes are maintained in ethereal solvents and toluene.

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“…Our interest lies in exploring phosphinates (R 2 PO 2 À ) as less conventional organic linker molecules that could be useful in the synthesis of coordination polymers. Relative to the classes of materials discussed previously, less attention has been given to phosphinates in extended materials (Al-Shboul et al, 2012;Rood et al, 2014). Compared to metal phosphonates, the acidbase chemistry of metal phosphinates may more closely resemble that of metal carboxylates.…”

Section: Introductionmentioning

confidence: 99%

One- and two-dimensional Cd^IIcoordination polymers incorporating organophosphinate ligands

Rood¹,

Boyer²,

Oliver³

2014

Acta Crystallogr C

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Reaction of cadmium nitrate with diphenylphosphinic acid in dimethylformamide solvent yielded the one-dimensional coordination polymer catena-poly[[bis(dimethylformamide-κO)cadmium(II)]-bis(μ-diphenylphosphinato-κ(2)O:O')], [Cd(C12H10O2P)2(C3H7NO)2]n, (I). Addition of 4,4'-bipyridine to the synthesis afforded a two-dimensional extended structure, poly[[(μ-4,4'-bipyridine-κ(2)N:N')bis(μ-diphenylphosphinato-κ(2)O:O')cadmium(II)] dimethylformamide monosolvate], {[Cd(C12H10O2P)2(C10H8N2)]·C3H7NO}n, (II). In (II), the 4,4'-bipyridine molecules link the Cd(II) centers in the crystallographic a direction, while the phosphinate ligands link the Cd(II) centers in the crystallographic b direction to complete a two-dimensional sheet structure. Consideration of additional π-π interactions of the phenyl rings in (II) produces a three-dimensional structure with channels that encapsulate dimethylformamide molecules as solvent of crystallization. Both compounds were characterized by single-crystal X-ray diffraction and FT-IR analysis.

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Linear alkaline earth metal phosphinate coordination polymers: synthesis and structural characterization

Cited by 7 publications

References 35 publications

Metal-binding motifs of alkyl and aryl phosphinates; versatile mono and polynucleating ligands

Metal-binding motifs of alkyl and aryl phosphinates; versatile mono and polynucleating ligands

Synthesis and Oligonuclear Structures of Strontium and Barium Complexes with Protonated and Deprotonated N-Mesityl-P,P-diphenylphosphinic Amide Ligands

One- and two-dimensional Cd^IIcoordination polymers incorporating organophosphinate ligands

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Linear alkaline earth metal phosphinate coordination polymers: synthesis and structural characterization

Cited by 7 publications

References 35 publications

Metal-binding motifs of alkyl and aryl phosphinates; versatile mono and polynucleating ligands

Metal-binding motifs of alkyl and aryl phosphinates; versatile mono and polynucleating ligands

Synthesis and Oligonuclear Structures of Strontium and Barium Complexes with Protonated and Deprotonated N-Mesityl-P,P-diphenylphosphinic Amide Ligands

One- and two-dimensional CdIIcoordination polymers incorporating organophosphinate ligands

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One- and two-dimensional Cd^IIcoordination polymers incorporating organophosphinate ligands