Crystal and molecular structure of dichloro-1- diphenylphosphino-2-diethylaminoethanemercury(II) at 138 K

Gupta, P. K. Sen; Houk, Larry W.; Helm, D. van der; Hossain, M. B.

doi:10.1016/s0020-1693(00)91018-1

Cited by 9 publications

(8 citation statements)

References 17 publications

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“…Table 1 contains pertinent bond lengths and angles of structurally characterised complexes of the type [MX 2 (Py) 2 ], [MX 2 (PPh 3 ) 2 ] and [MX 2 (dppf)] (dppf = 1,1¢-bis(diphenylphosphino)ferrocene, M = Zn, Cd, Hg; X = Cl, Br, I), together with data of the few known relevant P,Nchelates. 11- 31 Most of these complexes are four-coordinate and exhibit a distorted pseudo-tetrahedral structure. There are just five exceptions, viz.…”

Section: Resultsmentioning

confidence: 99%

“…The 31 P NMR signal remains essentially unshifted in the case of Zn II , indicating no substantial Zn-P bonding in solution. While broad 31 P NMR signals were observed for cadmium complexes of 1, indicative of dynamic processes close to the coalescence point, no 31 P NMR signal was detected for [CdBr 2 (2)], which is therefore in the coalescence regime. The strongest M-P interaction occurs in the case of [HgBr 2 (2)], as is reflected by the largest Dd value and the observation of metal-phosphorus coupling for this compound.…”

Section: Complexes With [Fementioning

confidence: 95%

“…1.1 ppm), which agrees well (12) 2.6775( 6) with the notion based on the HSAB principle that among the divalent Group 12 metals the strongest interaction with pyridine type donors is exhibited by Zn II , both partners being borderline between hard and soft. 37a The shift observed for the 31 P NMR signal with respect to non-coordinated 1 is very small in the case of the zinc complexes (Dd £ 3.7 ppm). It is moderately larger for the cadmium complexes (Dd ≥ 9.7 ppm) and substantially larger for the mercury complexes, where low-field shifts of up to ca.…”

Section: Complexes With [Fe(c 5 H 4 -Pph 2 )(C 5 H 4 -2-py)] (1)mentioning

confidence: 99%

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The coordination behaviour of ferrocene-based pyridylphosphine ligands towards ZnII, CdII and HgII

et al. 2011

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The reaction of Group 12 metal dihalides MX(2) with the P,N-ligands [Fe(C(5)H(4)-PPh(2))(C(5)H(4)-2-py)] (1) (2-py = pyrid-2-yl), [Fe(C(5)H(4)-PPh(2))(C(5)H(4)-CH(2)-2-py)] (2) and [Fe(C(5)H(4)-PPh(2))(C(5)H(4)-3-py)] (3) (3-py = pyrid-3-yl) was investigated. For a 1 : 1 molar ratio of MX(2) and the respective ligand, three structure types were found in the solid state, viz. chelate, cyclic dimer and chain-like coordination polymer. The M(II) coordination environment is distorted pseudo-tetrahedral in each case. The P-M-N angle is much larger in the chelates (≥119°) than in the ligand-bridged structures (≤109°). 1 prefers the formation of chelates [MX(2)(1-κ(2)N,P)]. 3 forms coordination polymers [MX(2)(μ-3)](n). With the more flexible 2 all three structure types can occur. Dynamic coordination equilibria were observed in solution for the molecular complexes obtained with 1 and 2. NMR data indicate that the N- and P-donor sites interact most strongly with Zn(II) and Hg(II), respectively. While the formation of bis(phosphine)mercury complexes (soft-soft) was easily achieved, no bis(pyridine)zinc complex (borderline-borderline) could be obtained, which is surprising in view of the HSAB principle.

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Section: Resultsmentioning

confidence: 99%

Section: Complexes With [Fementioning

confidence: 95%

Section: Complexes With [Fe(c 5 H 4 -Pph 2 )(C 5 H 4 -2-py)] (1)mentioning

confidence: 99%

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The coordination behaviour of ferrocene-based pyridylphosphine ligands towards ZnII, CdII and HgII

et al. 2011

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“…In the crystal structure of a P,O-chelate complex, trans-[Hg{Ph 2 PNP(O)Ph 2 -P,O} 2 ], the Hg atom was found to have a square planar geometry [7]. The complexes of mercury(II) with other unsymmetrical phosphines containing P, N [8] and P, S [9] donors have also been studied. The crystal structures of [Cl 2 (Ph 2 PCH 2 CH 2 NEt 2 )Hg] [8] and [{Ph 2 PCH 2 P(S)}HgI 2 ] [10] revealed a chelate mode of coordination with the mercury atom having a distorted tetrahedral geometry.…”

Section: Introductionmentioning

confidence: 99%

“…The complexes of mercury(II) with other unsymmetrical phosphines containing P, N [8] and P, S [9] donors have also been studied. The crystal structures of [Cl 2 (Ph 2 PCH 2 CH 2 NEt 2 )Hg] [8] and [{Ph 2 PCH 2 P(S)}HgI 2 ] [10] revealed a chelate mode of coordination with the mercury atom having a distorted tetrahedral geometry. It is apparent that the presence of different donor atoms in the same ligand induces different geometries and structures in the Hg(II) complexes.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, crystal structures and spectra of Hg(II)-1,2-bis(diphenylphosphino)ethane monoxide complexes: Monomer and polymer formation

Mothi¹,

Neels²,

Stœckli-Evans³

et al. 2007

Polyhedron

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The reaction of mercury(II) halides with 1,2-bis(diphenylphosphino)ethane monoxide (dppeO) in 1:1 molar ratio yielded P,Ocoordinated polymers having the empirical formula [HgX 2 (dppeO)] n [X = Cl (1), Br (2), I (3)]. In contrast, the reaction between the same reactants in a 1:2 molar ratio yielded the P, P-coordinated monomeric complexes, HgX 2 (dppeO) 2 [X = Cl (4), Br (5), I (6)]. The structures of 2, 3, 4 and 5 have been characterized crystallographically. The results indicate that the geometry around the mercury atom in each of these molecules is tetrahedral with considerable distortion. The 31 P NMR spectra of the 1:1 complexes indicate the dissociation of the Hg-O bond in solution.

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³¹P‐NMR and X‐Ray Studies of the Complexes [HgX₂ (1)]. (1=2, 11‐bis (diphenylphosphinomethyl)benzo [c]phenanthrene, X=Cl, I)

Kunz¹,

Pregosin²,

Camalli

et al. 1983

Helvetica Chimica Acta

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SummaryThe 31PI 'HI-NMR characteristics of the complexes [HgX2 (1) The ' J ( 199Hg, 31P) values increase in the order CN < I < SCN < Br < C1< NO3. The two molecular structures show a distorted tetrahedral geometry about mercury. Pertinent bond lengths and bond angles from the X-ray analysis are as follows:Hg-P=2.485(7) A and 2.509(8) A, Hg-C1=2.525(8) A and 2.505(10) A, P-Hg-P = 125.6 (3)", Cl-Hg-Cl= 97.0(3)' for [HgC12(1)] and Hg-P= 2.491 (10) A and 2.500 (1 1) A, Hg-I = 2.858 ( 5 ) A and 2.832 (3) A, P-Hg-P = 146.0(4)", I-Hg-I = 116.9(1)' for [Hg12(1)]. The equation, derived previously, relating 1J('99Hg, 31P) and the angles P-Hg-P and X-Hg-X is shown to be valid for 1.1. Introduction. -There are a number of reports concerned with the 31P-NMR characteristics of trigonal and tetrahedral phosphine complexes of Hg (11) [ 1-91. We have recently reported 31P-NMR and X-ray structural data for complexes of the type [HgX2 (PPh3)2] [lo] and find that the values 1J('99Hg, 31P) and the molecular structures for these species are markedly dependent on the anion X. An increase in the value 'J(*99Hg, 31P) is associated with an increase in the P-Hg-P bond angle and Hg-X bond length and/or a decrease in the Hg-P bond length and X-Hg-X angle. The molecular geometry approaches a tetrahedron when the anion X is a strong donor, such as I-or CN-, and distorts significantly when the anion is weakly coordinated, e.g. the P-Hg-P angle for [Hg (N03)2(PPh3)2] is 132", the 0-Hg-0 angle is 70". We have utilized the structural data as a basis for extended Hiickel calculations [lo] and found that the one-bond Hg, P-coupling is more sensitive to the P-Hg-P angle than the Hg-P distance. Given this observation we

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Crystal and molecular structure of dichloro-1- diphenylphosphino-2-diethylaminoethanemercury(II) at 138 K

Cited by 9 publications

References 17 publications

The coordination behaviour of ferrocene-based pyridylphosphine ligands towards ZnII, CdII and HgII

The coordination behaviour of ferrocene-based pyridylphosphine ligands towards ZnII, CdII and HgII

Synthesis, crystal structures and spectra of Hg(II)-1,2-bis(diphenylphosphino)ethane monoxide complexes: Monomer and polymer formation

³¹P‐NMR and X‐Ray Studies of the Complexes [HgX₂ (1)]. (1=2, 11‐bis (diphenylphosphinomethyl)benzo [c]phenanthrene, X=Cl, I)

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Crystal and molecular structure of dichloro-1- diphenylphosphino-2-diethylaminoethanemercury(II) at 138 K

Cited by 9 publications

References 17 publications

The coordination behaviour of ferrocene-based pyridylphosphine ligands towards ZnII, CdII and HgII

The coordination behaviour of ferrocene-based pyridylphosphine ligands towards ZnII, CdII and HgII

Synthesis, crystal structures and spectra of Hg(II)-1,2-bis(diphenylphosphino)ethane monoxide complexes: Monomer and polymer formation

31P‐NMR and X‐Ray Studies of the Complexes [HgX2 (1)]. (1=2, 11‐bis (diphenylphosphinomethyl)benzo [c]phenanthrene, X=Cl, I)

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³¹P‐NMR and X‐Ray Studies of the Complexes [HgX₂ (1)]. (1=2, 11‐bis (diphenylphosphinomethyl)benzo [c]phenanthrene, X=Cl, I)