Vibrational Spectroscopic Investigation of the Hofmann-type Clathrates: M(piperidine)2Ni(CN4. G (M=Co, Ni or Cu; G = benzene derivatives)

Infrared spectra of M(piperidine)₂Ni(CN)₄.0.5G (M=Co, Ni or Cu;G= chlorobenzene, 1,2-dichlorobenzene or 1,3-dichlorobenzene; M=Co or Ni;G=1,4-dichlorobenzene) compounds are reported. The piperidine molecules inthe host permit the inclusion of bulky guest molecules. The spectral featuressuggest that the compounds are similar in structure to the Hofmann-type clathrates.     

FT-IR Spectroscopic Study of M(1,2-Ethanedithiol)Ni(CN)4·Benzene (M=Co,Cd) Clathrates

New Hofmann-ethanedithiol-type clathrates, M(1,2-Ethanedithiol)Ni(CN)₄·Benzene (M=Cd,Co), have been obtained in the powdered form. By vibrational spectroscopy of these two new compounds, it is exhibited that their structures are similar to those of the other Hofmann-type clathrates.     

Vibrational Spectroscopic Studies on the Hofmann Type Clathrates: M(1,6-diaminohexane)Ni(CN) 4 .G (M = Co, Ni or Cd; G = chlorobenzene, 1,2-, 1,3- or 1,4-dichlorobenzene)

New Hofmann-diaminohexane(dahxn)-type clathrates of the form M(1,6-dahxn)Ni(CN)₄.G (M = Co, Ni or Cd; G = chlorobenzene, 1,2-, 1,3 or 1,4-dichlorobenzene) were prepared inpowder form and their infrared spectra are reported. The spectral data suggest that these compounds are similar in structure to those of the Hofmann-diam-type clathrates. Their structure consists of planar polymeric layers, {M–Ni(CN)₄}, formedfrom Ni(CN)₄ anions coordinated to the bridging 1,6-diaminohexane molecules bound directly to the metal (M). The M atoms are bound to four N atoms of the CN ions and, the Ni atoms are surrounded by four C atoms of the CN groups in a square-planar layer.     

Investigation of Host–Guest Interactions in the Hofmann-daddn-type Clathrates: M(1,12-diaminododecane)Ni(CN) 4 .G (M = Co, Ni or Cd; G = toluene, m-xylene, o-xylene or p-xylene)

New Hofmann-diaminododecane-type clathrates of the form M(1,12-diaminododecane) Ni(CN)₄?G (M = Co, Ni or Cd; G = toluene, m-xylene, o-xylene or p-xylene) have been prepared in powder form and their infared spectra are reported. The spectral data suggest that the host–guest frame-works of these compounds are similar in structure to other Hofmann-diam-type clathrates.     

Vibrational spectroscopic studies on the en-Td-type benzene clathrates: M(ethylenediamine)M′(CN)4·2C6H6 (M=Mn or Cd,M′=Cd or Hg)

IR spectra of Mn(en)M(CN)₄·2C₆H₆ (M=Cd or Hg), and IR and Raman spectra of Cd(en)M(CN)₄·2C₆H₆ (M=Cd or Hg) clathrates are reported. The spectral features suggest that the first two compounds are similar in structure to the later two Td-type clathrates.     

Vibrational Spectroscopic Studies on the Hofmann-dabn-Type Benzene Clathrates: M(1,4-diaminobutane)Ni(CN)4° 1.5C6H6 (M = Mn, Fe, Co, Ni or Cd)

IR spectra of M(1,4-diaminobutane)Ni(CN)4° 1.5C6H6 (M = Mn, Fe, or Co), and IR and Raman spectra of M(1,4-diaminobutane)Ni(CN)4° 1.5C6H6 (M = Ni or Cd) clathrates are reported. The spectral features suggest that the compounds are similar in structure to the Hofmann-dabn-type clathrates.     

Vibrational Spectroscopic Study of [1,2-bis(4-pyridyl)ethane]metal(II) Tetracyanonickelate(II). 2 m-Xylene Clathrates

Four new Hofmann-type clathrates of the form M(bpa)₂Ni(CN)_4· 2m-xylene (M = Mn , Fe , Co and Ni; bpa = 1,2-bis(4-pyridyl)ethane) have been synthesized and characterized by vibrational spectroscopy. The M(bpa)₂Ni(CN)₄ (M = Fe and Co) host structure is similar to the classical Hofmann-type host framework composed of layers of a two dimensional catena-metal tetra--cyanonickelate(II) network, but in M(bpa)₂Ni(CN)₄ (M = Mn and Ni), the Ni(CN)₄ moiety behaves as a bidentate –[NC-Ni(CN)₂-CN–]– unit in the host framework.     

Vibrational spectroscopic studies on the hofmann-Td-type clathrates: M(NH3)2M′(CN)4·2C6H6 (M=Mn or Cd and M′=Cd or Hg0

IR spectra of Mn(NH₃)₂M(CN)₄·2C₆H₆ (M=Cd or Hg), and IR and Raman spectra of Cd(NH₃)₂M(CN)₄·2C₆H₆ (M=Cd or Hg) are reported. The spectral data suggest that the former two compounds are similar in structure to the latter two Td-type clathrates.     

Infrared Spectroscopic Study on the Hofmann-dadn-type and the Td-dahxn-type clathrates

Infrared spectra of M(1,10-diaminodecane)Ni(CN)₄ · 1,5 G (M=Co, Ni or Cd; G=o-xylene, m-xylene, p-xylene) and Cd(l,6-diaminohexane)M(CN)₄ · C₆H₆ (M=Cd or Hg) clathrates are reported. The 1,10-diaminodecane and 1,6-diaminohexane molecules in the host permit the inclusion of bulky guest molecules. The spectral data of clathrates were compared with those of the corresponding host. The spectral features suggest that these compounds are similar in structure to other Hofmann-type and Hofmann-T_d type clathrates, respectively.     

Infrared Spectroscopic Study on the Hofmann Td-Type Clathrates: Mn(NH3)2M(CN)4·2 C6H5NH2 (M = Zn, Cd or Hg)

Infrared spectra of Mn(NH₃)₂M(CN)₄·2C₆H₅NH₂ (M = Zn, Cd or Hg) are reported. The spectral data suggest that these compounds are similar in structure to Hofmann-T_d-type clathrates.     

An Infrared Spectroscopic Study on the Hofmann-diam-type 1,12-Diaminododecanemetal(II) Tetracyanonickelate(II)-aromatic Guest Clathrates: M(H2N(CH2)12NH2)Ni(CN)4ċG(M=Co, Ni or Cd; G = Benzene, Naphthalene, Anthracene, Phenanthrene or Biphenyl)

Three Hofmann-diaminododecane-type clathrates of the form M(1,12-diaminododecane) Ni(CN)₄G (M = Co, Ni or Cd; G = benzene, naphthalene, anthracene, phenanthrene or biphenyl) have been prepared in powder form. The 1,12-diaminododecane molecules in the host lattice permit the inclusion of bulky guest molecules. The spectral features suggest that these compounds are similar in structure to the other Hofmann-diam-type clathrates.     

Vibrational Spectroscopic Studies on the tn-Td-Type Mn(tn)Zn(CN)4_2C6H6 and the Chelated tn-Td-Type Zn(tn)Zn(CN)4_2C6H6 Clathrates

IR spectra of Mn(trimethylenediamine)Zn(CN)₄2C₆H₆ and IR and Raman spectra of Zn(trimethylenediamine)Zn(CN)₄_2C₆H₆ are reported. The spectral data suggest that the host frameworks of these compounds are similar to those of the tn-Td-type Cd(trimethylenediamine)M(CN)₄_2benzene (M = Cd or Hg) and the chelated pn-Td-type Cd(propylenediamine)Cd(CN)₄_1,2-dichloro-ethane clathrates, respectively.     

Vibrational Spectroscopic Investigations of M(Imidazole)2Ni(CN)4·2 Dioxane Clathrates

Four new clathrates of the formula M(Im)2Ni(CN)4·2·Dioxane (where M = Co, Ni, Cu, Cd; Im = Imidazole) have been prepared in powder form and their FT-IR and laser-Raman spectra are reported for the first time. These clathrates are analogues to the previously reported classical Hofmann type clathrates except for the copper clathrate. The Cu clathrate has different spectral features in comparison with its analogues due to the Jahn-Teller effect.     

Infrared Spectroscopic Study of the Hofmann-daon-Type Clathrates : M(1,8-diaminooctane)Ni(CN)4⋅G (M=Co, Ni or Cd; G=Aromatic Guest Molecules)

Infrared spectra of M(1,8-diaminooctane)Ni(CN)4G (M= Co, Ni or Cd; G=benzene, chlorobenzene, toluene, p-xylene, naphthalene or biphenyl) compounds are reported. The 1,8-diaminooctane molecules in the host permit the inclusion of bulky guest molecules. The spectral features suggest that the compounds are similar in structure to the Hofmann-type clathrates.     

FT-IR spectroscopic investigation of transition metal (II) 2-aminopyridine tetracyanonickelate complexes

A series of Hofmann-type clathrate host molecules containing two 2-aminopyridine (2-Apy) groups attached to transition metal (II) (M) tetracyanonickelate frame, with the formula: M(2Apy)₂Ni(CN)₄ (where M=Mn, Co, Cu or Zn), have been synthesised for the first time. Their FT-IR spectra are reported in the 400–4000 cm⁻¹ region. The spectral features suggest that the compounds are substantially isostructural to that of already known Hofmann type pyridine complex; M(py)₂Ni(CN)₄. Moreover, 2Apy pyridine molecules are found to involve coordination through the ring nitrogen. The coordination effect on the 2Apy modes was analysed.     

An Infrared Spectroscopic Study on the Hofmann T d -Type Clathrates: M(Imidazole) 2 M'(CN) 4 .2C 6 H 6

Infrared spectra of M (Imidazole)2 M' (CN)₄ 2C₆H₆ (M = Mn, Co,Ni, Cd; M' = Zn, Cd) are reported. The spectral data suggest that the clathratesare similar in host structure to of Hofmann T_d-type clathrates.     

Reactions of the carbonyl complexes M(CO)3(L)3 (L = py,M = Mo,W; L = NH3, M = Mo) and M(CO)4(2-Mepy)2 (M = Mo,W) with HgX2 (X = Cl,CN, SCN)

The reactions of the substituted Group VI metal carbonyls of the type M(CO)₄(2-Mepy)₂ (M = Mo, w) and M(CO)₃(L)₃ (L = py, M = Mo, W; L = NH₃, M = Mo) with mercuric derivatives HgX₂ (X = Cl, CN, SCN) have given rise to three series of tricarbonyl complexes: M(CO)₃(py)HgCl₂ · 1/2HgCl₂ (M = Mo, W); 2[M(CO)₃(L)]Hg(CN)·nHg(CN)_x (L = py, M = Mo, W, n = $\text{1}\text{2}$, × = 2; L = 2- Mepy, × = 1; M = Mo, n = 3; M = W, n = 1); and [M(CO)₃(L)Hg(SCN)₂ · nHg(SCN)₂] (L = py, M = Mo,W, n = 0; L = 2-Mepy, M = Mo, W, n = $\text{1}\text{2}$; L = NH₃, M = Mo, n = 0) depending on which mercuric compound is employed. All the reactions with Hg(SCN)₂ give isolable products whereas those with Hg(CN)₂ and HgCl₂ did so far only the reactions with [M(CO)₄(2-Mepy)₂] and M(CO)₃(py)₃. The greater reactivity of Hg(SCN)₂ than of Hg(CN)₂ and HgCl₂ is consistent with the various acceptor capacities of the groups bonded to the mercury atom.The reactions studied always involve displacement of the N-donor ligand of the original complex and partial or total displacement of the halide or pseudohalide groups of the mercury compound to give in all cases compounds containing MHg bonds. In addition, elimination of a CO group in the tetracarbonyl complexes M(CO)₄(2-Mepy)₂occurs.     

Infrared spectroscopic studies of some piperidine metal(II) clathrates: M(C5H11N)2Ni(CN)4·G (M = Co,Ni; G = m-xylene,p-xylene or o-xylene; M = Ni; G = dioxane)

IR spectra of M(C₅H₁₁N)₂Ni(CN)₄·G (M=Co, Ni; G=o-, m- or p-xylene; M=Ni; G=dioxane) are reported. These clathrates are analogues to the previously reported classical Hofmann-type clathrates.     

Synthesis,spectroscopic, thermal,crystal structure properties and characterization of new Hofmann-type-like clathrates with 4-aminopyridine and water

In this study, synthesis of two new heteronuclear tetracyanonickelate(II) clathrates based on 4-aminopyridine (4AP) and guest water (H₂O) molecule and investigation of their structural properties were reported. These clathrates were characterized by using vibration spectroscopy, elemental, thermal analysis and single crystal X-ray diffraction (SC-XRD) techniques. Examining the elemental and spectral data of these clathrates, it was observed that the formulas [Zn(II)(4AP)₂Ni(µ-CN)₂(CN)₂]·6H₂O and [Cu(II)(4AP)₄Ni(µ-CN)₂(CN)₂]·H₂O were defined their structures. General information about the structural properties of these clathrates in single crystal form has been obtained by considering the changes in the characteristic peaks of the cyanide group and the 4AP that formed them. The thermal behaviors of these clathrates were obtained by examining the temperature-dependent changes of their masses. The magnetic susceptibilities of these clathrates in single crystal form were measured with a Gouy balance. According to the data obtained using SC-XRD technique, the heterometallic [Zn(II)(4AP)₂Ni(µ-CN)₂(CN)₂]·6H₂O compound has Cmcm and the heterometallic [Cu(II)(4AP)₄Ni(µ-CN)₂(CN)₂]·H₂O compound has crystal structures in the C2 / c space group.     

Vibrational Spectroscopic Studies on the Td-type Adeninemetal(II)tetracyanometallate(II) Benzene Clathrates: M(ad)2M'(CN)4.C6H6 (M = Mn or Cd, M' = Cd or Hg)

IR spectra of Mn(adenine)₂M(CN)₄.C₆H₆ (M=Cd or Hg), andIR and Raman spectra of Cd(adenine)₂M(CN)₄.C₆H₆(M=Cd or Hg) are reported. The spectral data suggest thatthe host frameworks of these compounds are similarto those of the Hofmann-T_d-type and the adeninecoordination is via N(10).