Novel bicyclic hexanuclear copper(I) aggregate: Structure and solid state 31P CPMAS NMR spectra of [(Cu3L3)2] and [Cu(PPh3)2L] complexes of N-(diisopropoxythiophosphinyl)-N′-phenylthiourea (HL)

Sokolov, Felix D.; Babashkina, Maria G.; Fayon, Franck; Rakhmatullin, Aydar; Safin, Damir A.; Pape, Tania; Hahn, F. Ekkehardt

doi:10.1016/j.jorganchem.2008.10.010

Cited by 31 publications

(32 citation statements)

References 39 publications

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“…P and27 Al[57][58][59][60][61][62]54,15,16],63,65 Cu[26,27,[63][64][65],31 P-113,115 In[66,67],31 P-55 Mo [68], 31 P-101,99 Ru [69], 31 P-17 O [70], and 19 F-93 Nb [71]. These examples show a variety of situations with often strong dipolar/ quadrupolar cross-terms leading to complex spectra even in rather simple compounds.…”

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confidence: 99%

Detection and use of small J couplings in solid state NMR experiments

Massiot

Fayon

Deschamps

et al. 2009

Comptes Rendus. Chimie

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Over the years, solid-state nuclear magnetic resonance (NMR) spectroscopy has become an important tool for materials science, with its local point of view that is highly complementary to the structural information provided by diffraction techniques, electron microscopy, and molecular modeling, for example. As compared to other interactions that determine the spectral expression of the local structure of the observed nuclei in solid-state NMR experiments, the J coupling, characteristic of the chemical bonds, has received far less attention because of its being generally so small that it is masked in the line-widths. Nevertheless, the scalar or isotropic part of J couplings, which is not averaged by magic angle spinning (MAS), can be evidenced in many systems, and exploited to unequivocally characterize the extended coordination sphere. In a first step we describe the different experiments that permit the observation and the measurement of J couplings, even when dealing with quadrupolar nuclei. We then present new and recently-published results that illustrate the state of the art of NMR methodologies based on or intended for measuring J couplings in solids and the novel perspectives that they open towards better understanding of ordered and disordered materials at the subnanometric scale, a length scale that is otherwise difficult to access.

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confidence: 99%

Detection and use of small J couplings in solid state NMR experiments

Massiot

Fayon

Deschamps

et al. 2009

Comptes Rendus. Chimie

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“…Intermolecular hydrogen bonds are formed between the hydrogen atom of one PNH group and the sulfur atom of the C=S group, and the same types of atoms of the two neighbouring molecules. As a result of the intermolecular hydrogen bonds (Table 4) (12) 1.578(6), [a] 1.583(6) [a] C-N(P) 1.377(2) 1.314(3) 1.333(3) 1.316(10), 1.312(11) [a] C-N 1.340 (2) 104.40(8), [a] 115.58(9) [a] Cu-S-C 107.21 (8) 106.88(9) 103.6(3), 108.5(3) [a] 104.30(9), 99.72 (9) [b]…”

Section: Resultsmentioning

confidence: 99%

“…The same type of anionic thiourea ligand was observed in the structure of polynuclear Cu I complexes. [1,3,7,[9][10][11] The Cu1···Cu2 distance of 2.8355(4) Å is slightly longer than the sum of two van der Waals radii of Cu I (2.80 Å). [26] In the crystal, two molecules of the complexes 1 and 3-5 form centrosymmetric dimers as a result of intermolecular hydrogen bonds (Table 4).…”

Section: Resultsmentioning

confidence: 99%

“…In preceding papers we described heteroligand complexes of Cu I with a number of N-thiophosphorylated thioureas and thioamide RC(S)NHP(S)(OiPr) 2 [R = morpholin-4-yl, piperidin-1-yl, [1] (1-naphthyl)NH, [2] NH 2 (HL I ), [1,3] (pyridin-2-yl)NH, (pyridin-3-yl)NH, H 2 N-6-Py-2-NH, [4] Ph, Et 2 N, [5][6][7] (EtO) 2 P(O)CH 2 C 6 H 4 -4-NH, [8] MeNH, iPrNH, tBuNH, Me 2 N, PhNH, 2,6-Me 2 C 6 H 3 NH, 2,4,6-Me 3 C 6 H 2 NH [9][10][11] ] and triphenylphosphane or Ph 2 P-(CH 2 ) 1-3 PPh 2 and Ph 2 P(C 5 H 4 FeC 5 H 4 )PPh 2 . We also showed that the reactions of alkaline salts of the tetrakisScheme 1.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Characterisation and Luminescent Properties of Mixed‐Ligand Copper(I) Complexes Incorporating N‐Thiophosphorylated Thioureas and Phosphane Ligands

et al. 2010

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The potassium salts of H2NC(S)NHP(S)(OiPr)2 (HLI) or o‐C6H4[NHC(S)NHP(S)(OiPr)2]2 (H2LII) react with [Cu(PPh3)3I] or a mixture of CuI and Ph2P(CH2)1–3PPh2 or Ph2P(C5H4FeC5H4)PPh2 in aqueous EtOH/CH2Cl2 to give mononuclear complexes [Cu(PPh3)LI] (1), [Cu{Ph2P(CH2)2PPh2}LI] (2), [Cu{Ph2P(CH2)3PPh2}LI] (3) or [Cu{Ph2P(C5H4FeC5H4)PPh2}LI] (4), or dinuclear complexes [Cu2(Ph2PCH2PPh2)LI2] (5), [Cu2(PPh3)2LII] (6), [Cu2{Ph2P(CH2)2PPh2}2LII] (7), [Cu2{Ph2P(CH2)3PPh2}2LII] (8), [Cu2{Ph2P(C5H4FeC5H4)PPh2}2LII] (9) or [Cu2(Ph2PCH2PPh2)LII] (10). The structures of these compounds were investigated by 1H and 31P{1H} NMR, UV/Vis spectroscopy and elemental analysis. The crystal structures of H2LII, 1, 3–6, 8 and 10 were determined by single‐crystal X‐ray diffraction. The luminescent properties of complexes 1–10 in the solid state are reported.

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“…We suppose, that during the Ag I and Cu II cations extraction by HL 12 -HL 14 the formation of polynuclear structures is possible, as described elsewhere. 13,17,[19][20][21][22][23] Comparison of the transport properties of the thioamides HL 12 and HL 13 appears not to favour the former. The donor properties of the methyl substituent in HL 12 does not promote formation of stable coordination compounds with transition and post-transition metal ions, 24 whereas the p-acceptor substituent near the C=S fragment considerably increases the stability of the complexes formed.…”

Section: Resultsmentioning

confidence: 99%

Competitive bulk liquid membrane transport of some metal ions using RC(S)NHP(S)(OiPr)2 as ionophores. Unusual supramolecular “honeycomb” aggregate of the polynuclear copper(I) complex of H2NC(S)NHP(S)(OiPr)2

et al. 2009

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Competitive transport experiments involving metal ions from an aqueous source phase through a chloroform membrane into an aqueous receiving phase have been carried out using a series of N-(thio)phosphorylated (thio)amide and thiourea ligands as ionophores in the organic phase. The source phase contained equimolar concentrations of Co(II), Ni(II), Cu(II), Zn(II), Ag(I), Cd(II) and Pb(II) with the source and receiving phases being buffered at different pH. Good transport properties were observed for Ag(I) in the case of (13). The best extraction properties have been shown by (3)L(1), (3)L(8), (2)L(7), (3)L(9) and (3)L(11) which contain an unsubstituted nitrogen atom at the C[double bond, length as m-dash]S groups ((3)L(1) and (3)L(9)), or a third nitrogen atom, capable of participating in additional coordination ((3)L(8), (2)L(7) and (3)L(11)). Reaction of Cu(NO(3))(2).6H(2)O with the potassium salt of the N-thiophosphorylated thiourea NH(2)C(S)NHP(S)(OiPr)(2) formed a new supramolecular Cu(I) complex, [{Cu(6)((2)L(1))(6)}{Cu(3)((2)L(1))(3)}.4Me(2)CO] that contains both trinuclear and hexanuclear forms in its solid state structure, and in solution.

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Novel bicyclic hexanuclear copper(I) aggregate: Structure and solid state 31P CPMAS NMR spectra of [(Cu3L3)2] and [Cu(PPh3)2L] complexes of N-(diisopropoxythiophosphinyl)-N′-phenylthiourea (HL)

Cited by 31 publications

References 39 publications

Detection and use of small J couplings in solid state NMR experiments

Detection and use of small J couplings in solid state NMR experiments

Synthesis, Characterisation and Luminescent Properties of Mixed‐Ligand Copper(I) Complexes Incorporating N‐Thiophosphorylated Thioureas and Phosphane Ligands

Competitive bulk liquid membrane transport of some metal ions using RC(S)NHP(S)(OiPr)2 as ionophores. Unusual supramolecular “honeycomb” aggregate of the polynuclear copper(I) complex of H2NC(S)NHP(S)(OiPr)2

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