Structural, vibrational and solid state CP MAS 31P NMR spectroscopic studies of complexes of trimethylphosphine with copper(I) and silver(I) halides

Bowmaker, GA; Silva, E.N. de; Healy, Peter Conrad; Skelton, Brian W.; White, Allan H.

doi:10.1039/a808778d

Cited by 16 publications

(22 citation statements)

References 36 publications

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“…The In previous studies of coinage metal halide complexes we have shown that the primary factor that determines the number of metal-halogen vibrational bands is the number of distinct metalhalogen bond lengths. 14 Application of this principle to AgSCN suggests assignment of the bands at 234, 196, 133 and 116 cm -1 to three n(AgS) modes and one n(AgN) mode (Table 6). This assignment is supported by the fact that the far-IR spectrum of the b-polymorph of CuSCN, which has a more symmetrical crystal structure than that of AgSCN, with only one Cu-S and one Cu-N bond length, 15 shows only two bands (at 242, 203 cm -1 ) in the 250-110 cm -1 region in the far-IR.…”

Section: Infrared Spectroscopymentioning

confidence: 99%

1 : 1 complexes of silver(i) thiocyanate with (substituted) thiourea ligands

et al. 2009

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Syntheses and single crystal X-ray structural characterizations, together with infrared spectroscopic studies, are recorded for 1 : 1 adducts of silver(I) thiocyanate with thiourea ('tu') and N,N'-diethylthiourea ('detu' identical with (EtNH)(2)CS). The two complexes display novel and different polymeric forms. That formed with tu is a double-stranded form, comprising a pair of Ag(mu-S-tu)Ag(mu-... strands linked by pairs of mu-SCN anions, the whole array having quasi-2 symmetry about the polymer axis. The detu adduct takes the ionic form [Ag(detu)2](infinity|infinity)[Ag(SCN)2](infinity|infinity), both cation and anion being one-dimensional polymers lying in parallel, and both of the form ...Ag(mu-S-L)2Ag(mu-... (L = SCN or detu), disposed about crystallographic 4 axes. Redeterminations of the structures of AgSCN : tu, etu (1 : 2) ('etu' = ethylenethiourea, (CH2NH)2CS)) with quasi-trigonal silver atom environments (the etu adduct the more closely so), are also recorded as a basis for an IR spectroscopic characterization of the [(NCS)Ag(S-xtu)2] array. A mechanochemical/infrared study of the AgSCN:etu (1 : 1) system showed that no 1 : 1 complex exists in this case, the product being a mixture of the 1 : 2 complex and a novel 1 : 0.5 complex. The latter complex was prepared both mechanochemically and from solution, and characterized by infrared spectroscopy. Diagnostic ligand and metal-ligand bands in the IR and far-IR spectra are assigned for all of the complexes studied and for AgSCN and are discussed in relation to the structures of the complexes. The double degeneracy of the delta(SCN) mode of the coordinated thiocyanate is lifted and the first overtone of this band at gains intensity in the IR in the 1 : 1 complexes, behaviour that is not observed for the terminal bonding mode that is present in the 1 : 2 complexes.

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Section: Infrared Spectroscopymentioning

confidence: 99%

1 : 1 complexes of silver(i) thiocyanate with (substituted) thiourea ligands

et al. 2009

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“…In contrast, sterically less demanding phosphane ligands preferred the formation of tetrameric complexes. In this case, two different structures are possible, a pseudo-cubane structure 1 with triply-bridging halides [Cu(µ 3 -X)PR 3 ] 4 which was observed for PMe 3 (X = I) (Bowmaker et al, 1999), PEt 3 (X = Cl, Br, I) (Churchill & Kalra, 1974;Churchill, DeBoer, Donovan, 1975;Churchill, DeBoer, Mendak, 1975), t-Bu 3 P (X = Br, I) (Goel & Beauchamp, 1983;Medina et al, 2005), PMePh 2 (X = I) (Churchill & Rotella, 1977), and PPh 3 (X = Br, Cl, I) or an open-step tetramer 2 which was observed for PPh 3 (X = Br, I) (Churchill & Kalra, 1973;Churchill & Kalra, 1974;Churchill, DeBoer, Donovan, 1975;Churchill, DeBoer, Mendak, 1975; (Fig. 1).…”

Section: Commentmentioning

confidence: 81%

“…For general background to this work, see: Ainscough et al (2001); Alyea et al (1985); Baker et al (1994); Barron et al (1984); Bowmaker et al (1989Bowmaker et al ( , 1992Bowmaker et al ( , 1994Bowmaker et al ( 1999Bowmaker et al ( , 2002; Churchill & Kalra (1973, 1974; Churchill, DeBoer & Donovan (1975) ;Churchill, DeBoer & Mendak (1975); Churchill & Rotella (1977, 1979; ; ; Gill et al (1976); Goel & Beauchamp (1983); Hadjikakou et al (1993); Herberhold et al (2003); Hermann et al (2001); Jansen (1987); Krause (2002); Mann et al (1936); Medina et al (2005); Moers & Op Het Veld (1970); Ramaprabhu et al (1993Ramaprabhu et al ( , 1998; Schwerdtfeger et al (2004); Soloveichik et al (1992); Wells (1936); Whitesides et al (1971). The CuÁ Á ÁCu distance is markably short as compared with the reported distances of other tetranuclear copper phosphane complexes (Medina et al, 2005).…”

Section: Related Literaturementioning

confidence: 99%

Tetra-μ₃-iodido-tetrakis[(tri-n-butylphosphane-κP)copper(I)]

Klenk¹,

Frey²,

Bubrin³

2014

Acta Cryst E

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The title complex, [Cu4I4(C12H27P)4], crystallizes with six molecules in the unit cell and with three independent one-third molecule fragments, completed by application of the relevant symmetry operators, in the asymmetric unit. The tetranuclear copper core shows a tetrahedral geometry (site symmetry 3..). The I atoms also form a tetrahedron, with I⋯I distances of 4.471 (1) Å. Both tetrahedra show an orientation similar to that of a pair of self-dual platonic bodies. The edges of the I-tetrahedral structure are capped to the face centers of the Cu-tetrahedron and vice versa. The Cuface⋯I distances are 2.18 Å (averaged) and the Iface⋯Cu distances are 0.78 Å (averaged). As a geometric consequence of these properties there are eight distorted trigonal–bipyramidal polyhedra evident, wherein each trigonal face builds up the equatorial site and the opposite Cu⋯I positions form the axial site. As expected, the n-butyl moieties are highly flexible, resulting in large elongations of their anisotropic displacement parameters. Some C atoms of the n-butyl groups were needed to fix alternative discrete disordered positions.

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“…In polymeric [Ag 4 Cl 4 (PMe 3 ) 3 ] (Bowmaker et al, 1999), the AgÐP distance is 2.362 (4) A Ê , though the coordination is not strictly two-coordinate. Likewise, for analogous gold complexes of the type [L 2 Au]Y, the only truly two-coordinate example found without signi®cant anion interactions was [(Me 3 P) 2 Au]Cl (Angermaier et al, 1994), with AuÐP 2.2304 (1) A Ê and PÐAuÐP 175.4 (1) ; the AuÁ Á ÁCl distance of 3.167 (1) A Ê indicated a weak`ion-pair contact' interaction.…”

Section: Commentmentioning

confidence: 99%

“…For comparison, the cone angles were calculated for the AgÐPMe 3 moiety in some other known complexes of Ag with trimethylphosphine. In the polymeric complexes [Ag 4 Cl 4 (PMe 3 ) 3 ] (Bowmaker et al, 1999) and [Ag(PR 3 ) 2 ] 2 [Ni(mnt) 2 ] (mnt is maleonitriledithiolate; Youm et al, 2000), similar cone angles of 116 and 115 , respectively, re¯ect the absence of steric congestion. The cone angle in polymeric [Me 3 PAgCCSiMe 3 ], which has adjacent phosphine ligands [PÐAgÐP 113.33 (9) ; Brasse et al, 1996], is 111 .…”

Section: Commentmentioning

confidence: 99%

Bis(trimethylphosphine)silver(I) hexafluorophosphate

Alyea

Kannan

Meehan

2002

Acta Crystallogr C Cryst Struct Commun

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In the title two-coordinate silver compound, [Ag(C(3)H(9)P)(2)]PF(6), the cation has crystallographically imposed mirror symmetry, and approximates very closely to 3m (D(3d)) symmetry with fully staggered methyl groups in the solid state. The Ag atom has a nearly linear coordination geometry, with a P[bond]Ag[bond]P angle of 178.70 (4) degrees. The Ag[bond]P bond lengths are 2.3746 (12) and 2.3783 (12) A, which are significantly longer than the Au[bond]P bond length of 2.304 (1) A in the analogous two-coordinate gold cation. The lack of intramolecular steric effects within the present cations containing trimethylphosphine (cone angle 118 degrees), compared with those in known cations containing trimesitylphosphine (cone angle 212 degrees), provides a better comparison of M[bond]P distances and thus more conclusive evidence that Au really is smaller than Ag.

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Structural, vibrational and solid state CP MAS 31P NMR spectroscopic studies of complexes of trimethylphosphine with copper(I) and silver(I) halides

Cited by 16 publications

References 36 publications

1 : 1 complexes of silver(i) thiocyanate with (substituted) thiourea ligands

1 : 1 complexes of silver(i) thiocyanate with (substituted) thiourea ligands

Tetra-μ₃-iodido-tetrakis[(tri-n-butylphosphane-κP)copper(I)]

Bis(trimethylphosphine)silver(I) hexafluorophosphate

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Structural, vibrational and solid state CP MAS 31P NMR spectroscopic studies of complexes of trimethylphosphine with copper(I) and silver(I) halides

Cited by 16 publications

References 36 publications

1 : 1 complexes of silver(i) thiocyanate with (substituted) thiourea ligands

1 : 1 complexes of silver(i) thiocyanate with (substituted) thiourea ligands

Tetra-μ3-iodido-tetrakis[(tri-n-butylphosphane-κP)copper(I)]

Bis(trimethylphosphine)silver(I) hexafluorophosphate

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Tetra-μ₃-iodido-tetrakis[(tri-n-butylphosphane-κP)copper(I)]