Solution equilibria of tertiary phosphine complexes of copper(I) halides

Fife, Dennis J.; Moore, William M.; Morse, Karen W.

doi:10.1021/ic00180a011

Cited by 79 publications

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“…Nevertheless, such distortions within all these structures could be considered as normal due to the strain imposed by the six-membered chelate rings formed. [12] On the other hand, the distortions within the P-Cu-S angles observed for 2, with values differing by ca 23°, are somewhat larger than in 1. In contrast, the individual PCu-X angles (X = Cl, Br, C) in the three above compounds chosen for comparison, differ only slightly from each other, thus the situation in the present two structures can be associated with the orientation of the heterocyclic ring imposed by the C(42)-S-Cu angle.…”

Section: X-ray Structural Investigationsmentioning

confidence: 88%

Structural and Spectroscopic Properties of New Copper(I) Complexes with 1,1,1‐Tris(diphenylphosphanylmethyl)ethane and Heterocyclic Thiolates

et al. 2008

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Reactions of copper(I) halides with 1,1,1‐tris(diphenylphosphanylmethyl)ethane (triphos) in 1:1 molar ratio afforded mononuclear complexes of the type [CuX(triphos)] which on further treatment with one equivalent of the potassium thiolate salt of a heterocyclic thione gave rise to the formation of mixed‐ligand complexes of the formula [Cu(κ3‐triphos)(κ1‐thiolate)]. The molecular structures of [Cu(κ3‐triphos)(κ1‐py2S)]·C2H5OH (1) and [Cu(κ3‐triphos)(κ1‐pymt)] (2) have been established by single‐crystal X‐ray diffraction. The complexes adopt a rigid distorted tetrahedral geometry with the phosphane ligand acting in a tridentate chelating mode. The complexes are strongly luminescent in solution and in the solid state. The spectroscopic and electronic properties of the new copper(I) complexes have been computed by electronic structure computational techniques (TD‐DFT calculations), that contribute to the assignments of electronic spectra. The high‐energy absorptions in the absorption spectra of complexes 1 and 2, ranging from 210 to 270 nm, are assigned to MLCT/LLCT transitions and the same also holds true for the low‐energy absorptions found in the range 280 to 300 nm. In the lowest triplet excited state, T1, involved in the emission in the 456–502 nm range, the spin density is delocalized over the entire nuclear framework.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Section: X-ray Structural Investigationsmentioning

confidence: 88%

Structural and Spectroscopic Properties of New Copper(I) Complexes with 1,1,1‐Tris(diphenylphosphanylmethyl)ethane and Heterocyclic Thiolates

et al. 2008

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“…Future work will include the extension of studies considering related systems in order to wrap multinary chalcogenidometallate complexes and clusters by a bio-organic shell or to link them to each other through organic bridges with specific properties. [27] Cl 3 GeCH 2 CH 2 COOH, Cl 3 GeCMe 2 CH 2 -A C H T U N G T R E N N U N G COMe, [28] CuClPPh 2 Me, [29] and CuClA C H T U N G T R E N N U N G (PPh 3 ) 3 [30] were prepared according to the reported methods. CuCl, N 2 H 4 ·H 2 O and Na 2 S·9 H 2 O were purchased from Aldrich.…”

Section: Discussionmentioning

confidence: 99%

Synthesis and Reactivity of Functionalized Binary and Ternary Thiometallate Complexes [(RT)₄S₆], [(RSn)₃S₄]²⁻, [(RT)₂(CuPPh₃)₆S₆], and [(RSn)₆(OMe)₆Cu₂S₆]⁴⁻ (R=C₂H₄COOH, CMe₂CH₂COMe; T=Ge, Sn)

Fard

Xiong

Müller

et al. 2009

Chemistry A European J

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A series of compounds comprising functionalized thiometallate cages [(RT)4S6] (R terminated by COO(H) or COR groups), based on adamantane (T=Ge) or double-decker (T=Sn) type structures or [(RSn)3S4]2- anionic defect heterocubanes were synthesized and their reactions with 1) transition-metal compounds and 2) hydrazine derivatives were explored. Hence it was possible to generate functionalized ternary CuSnS or CuGeS clusters and to transfer COR ligands into CR(N-NH2) or CR(N-NHPh) terminal groups, respectively. The report provides the proof-of-principle for a directed functionalization and derivatization of chalcogenidometallate cages with respect to the formation of chalcogenidometallate-organic hybrid compounds containing M/E semiconductor nodes, as an alternative to the so far most prominent M/O combination in metal-organic frameworks. DFT investigations deliver further insight in the peculiarities of Ge/S versus Sn/S precursors and their products.

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“…It is not possible to deduce whether this exchange is inter-or intramolecular. However, since it is known that these kinds of complexes may undergo ligand dissociation in solution (26), it is quite possible that the exchange is intermolecular in nature. ' The species in solution at low temperature could have the dimeric structure found in the solid state.…”

Section: Imentioning

confidence: 99%

Complex formation between cuprous iodide and phenyl phosphine: a nuclear magnetic resonance and X-ray crystallographic study

Batchelor¹,

Birchall²,

Faggiani³

1985

Can. J. Chem.

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, 928 (1985). The X-ray crystal structure of di-p,-iodobis[bis(phenylphosphine)co~per(I)] has been determined: R, = 0.0460. The crystals were monoclinic, space group Cc, a = 10.625(2) A, b = 25.1 15(8) A, c = 1 1.361(2) A, P = 105.929(15)", fw = 821.28, and Z = 4. The molecular structure consists of two C U I ( C~H~P H~)~ units bridged via the iodines so that each copper achieves tetrahedral coordination. Nuclear magnetic resonance data provides evidence that the phenylphosphines remain coordinated in solution but undergo rapid exchange at room temperature. qui sont relites par les iodes d'une fa~on telle que chaque atome de cuivre atteint une coordination tCtraCdrique. Sur la base des donnCes de la rmn, on peut affirmer que, en solution, les phCnylphosphines restent coordinnkes mais qu'elles subissent un Cchange rapide a la temptrature ambiante.[Traduit par le journal] Introduction phine, arsine) appeared to be potentially useful for investigaAlthough basicity and donor ability are well known propertions concerning the relative importance of steric and electronic ties of trivalent compounds of the group 5 elements there has factors because a large number of X-ray crystallographic been relatively little investigation of the coordination chemistry studies have shown that the steric bulk of both the neutral of hydrides and organohydrides of these elements other than nitrogen. Presumably this is because the tertiary derivatives, especially the triphenyl compounds, are much easier to work with and much less susceptible to oxidation. While it is reasonable to expect that the coordination chemistry of primary and secondary phosphines will be very similar to that of tertiary derivatives potential differences do exist. For example, there is evidence for the dissociation of P-H bonds with resultant formation of phosphido complexes (1). Also it has been noted that the order of basicity for phosphines is

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Solution equilibria of tertiary phosphine complexes of copper(I) halides

Cited by 79 publications

References 0 publications

Structural and Spectroscopic Properties of New Copper(I) Complexes with 1,1,1‐Tris(diphenylphosphanylmethyl)ethane and Heterocyclic Thiolates

Structural and Spectroscopic Properties of New Copper(I) Complexes with 1,1,1‐Tris(diphenylphosphanylmethyl)ethane and Heterocyclic Thiolates

Synthesis and Reactivity of Functionalized Binary and Ternary Thiometallate Complexes [(RT)₄S₆], [(RSn)₃S₄]²⁻, [(RT)₂(CuPPh₃)₆S₆], and [(RSn)₆(OMe)₆Cu₂S₆]⁴⁻ (R=C₂H₄COOH, CMe₂CH₂COMe; T=Ge, Sn)

Complex formation between cuprous iodide and phenyl phosphine: a nuclear magnetic resonance and X-ray crystallographic study

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Solution equilibria of tertiary phosphine complexes of copper(I) halides

Cited by 79 publications

References 0 publications

Structural and Spectroscopic Properties of New Copper(I) Complexes with 1,1,1‐Tris(diphenylphosphanylmethyl)ethane and Heterocyclic Thiolates

Structural and Spectroscopic Properties of New Copper(I) Complexes with 1,1,1‐Tris(diphenylphosphanylmethyl)ethane and Heterocyclic Thiolates

Synthesis and Reactivity of Functionalized Binary and Ternary Thiometallate Complexes [(RT)4S6], [(RSn)3S4]2−, [(RT)2(CuPPh3)6S6], and [(RSn)6(OMe)6Cu2S6]4− (R=C2H4COOH, CMe2CH2COMe; T=Ge, Sn)

Complex formation between cuprous iodide and phenyl phosphine: a nuclear magnetic resonance and X-ray crystallographic study

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Synthesis and Reactivity of Functionalized Binary and Ternary Thiometallate Complexes [(RT)₄S₆], [(RSn)₃S₄]²⁻, [(RT)₂(CuPPh₃)₆S₆], and [(RSn)₆(OMe)₆Cu₂S₆]⁴⁻ (R=C₂H₄COOH, CMe₂CH₂COMe; T=Ge, Sn)