The new facial tripod ligand 3,3-bis(1-methylimidazol-2-yl)propionic acid and carbonyl complexes thereof containing manganese and rhenium (original) (raw)
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Inorganica Chimica Acta, 2011
The new N,N,O heteroscorpionate ligand 3,3-bis(1-vinylimidazol-2-yl)propionic acid (Hbvip) (5) was synthesised in five steps starting from 1-vinylimidazole. This ligand is closely related to 3,3-bis(1-methylimidazol-2-yl)propionic acid (Hbmip), but contains two vinyl linker groups which can be used for radical-induced polymerisation reactions. The j 3-N,N,O coordination behaviour of 5 was proven by the synthesis of the tricarbonyl complexes [Re(bvip)(CO) 3 ] (6), [Mn(bvip)(CO) 3 ] (7) and [Cu(bvip) 2 ] (8). To obtain good yields of 6, it was synthesised in water instead of THF. The ligand as well as all three complexes were characterised by X-ray crystallography. Copolymerisation of 5 with pure methyl methacrylate (MMA) or a combination of MMA and ethylene glycol dimethacrylate (EGDMA) led to the solid phases P1 and P2. Polymer-bound rhenium and manganese tricarbonyl complexes could be obtained by the reaction of deprotonated P1 with [MBr(CO) 5 ] (M = Re, Mn) and also by copolymerisation of 6 and 7 with MMA. In both cases, the facial tripodal binding behaviour was evidenced by IR spectra of the polymers. Furthermore, the content of metal incorporated in the polymers was determined by elemental analysis, AAS or ICP-OES measurements. Reaction of the deprotonated solid phase P1 with copper(II) chloride led to a blue solid-phase (P1-Cu). The UV-Vis absorption maximum of P1-Cu is found at 615 nm, which is almost identical to that found for 8. Thereby, it seems likely that P1 is flexible enough to form bisligand complexes with copper(II). This means that the copper centres act as a kind of crosslinking agents. In contrast, the heterogeneous reaction of P2 with copper(II) chloride yielded a lime green solid phase (P2-Cu). The bathochromic shift of the absorption maximum by 102 nm suggests one-sided bound copper centres.
Journal of Organometallic Chemistry, 2001
The coordination of the ligands bis(3,5-dimethylpyrazol-1-yl)acetate (bdmpza) and bis(pyrazol-1-yl)acetate (bpza) to Group VII metal carbonyls has been investigated. The compounds [LM(CO) 3 ], where M = Mn, Re and L=bpza, bdmpza (2a-3b), have been synthesised. The new complexes [(bdmpza)Mn(CO) 3 ] (2b), [(bpza)Re(CO) 3 ] (3a) and [(bdmpza)Re(CO) 3 ] (3b), and bis(pyrazol-1yl)acetic acid (1a) have been characterised by single-crystal X-ray analyses. Based on IR-spectroscopic and structural data the electronic properties of these ligands are compared with those of Tp, Tp Me2 , Cp and Cp*. The reaction of [(bdmpza)Re(CO) 3 ] (3b) with NOBF 4 afforded [(bdmpza)Re(CO) 2 (NO)]BF 4 (4).
Journal of Coordination Chemistry, 2016
A six-coordinate Mn(IV) complex, [Mn(H 2 L) 2 ] (1) [H 4 L = 2-methoxy-6-(tris(hydroxymethyl)methyliminomethyl)phenol], was synthesized and characterized by elemental analysis, single-crystal X-ray crystallography, FTIR, UV-Vis electronic absorption, and EPR spectroscopy. The single-crystal structural determination reveals that the complex crystallizes in tetragonal space group P4 1 2 1 2 and the tridentate Schiff base ligands are arranged in mer configuration chelating manganese, which exhibits as slightly distorted octahedral coordination sphere with a N 2 O 4 chromophore. Weak hydrogen bonding interactions of uncoordinated hydroxyl groups result in a 2-D supramolecular structure. The UV-Vis electronic absorption and IR spectral data of 1 have been compared with the results obtained by employing DFT and time-dependent density functional theory calculation using B3LYP, B3PW91, and MPW1PW91 functionals, with 6-31G (d-p) and LanL2MB basis sets. The results of these calculations are functional-dependent and, among those used, B3PW91 proved to better reproduce the experimental results.
European Journal of Inorganic Chemistry, 2005
A general synthetic route towards new tridentate, tripodal N,N,O ligands, bearing one carboxylate group and two of the biologically relevant imidazole moieties, is presented. The parent compounds of this new family of ligands, A[MIm 2 Pr] (1) and A[BenzMIm 2 Pr] (2) (A = H, K, Bu 4 N) were synthesized in two steps and high overall yield. The structures of HMIm 2 Pr (1a) and HBenzMIm 2 Pr (2a) were confirmed by Xray crystal structure determination, both molecules forming infinite one-dimensional hydrogen bonded chains. The synthetic route allows for the fine-tuning of the physical properties of both ligand systems, e.g., solubility and ease of crystallization. The capability of the two ligands to coordinate facially through all donor atoms was investigated and two isostructural mononuclear copper(II) complexes of the type [CuL 2 ] were obtained. Both [Cu(MIm 2 Pr) 2 ]·2H 2 O (3) and [Cu-(BenzMIm 2 Pr) 2 ]·3.12(H 2 O)·1.74(C 2 H 5 OH) (4) have been characterized by X-ray crystallography, ESI-MS, elemental [a]
Journal of organometallic …, 2002
The (alkynylcarbyne)tungsten complexes [L 3 (CO) 2 W C C C R] (3a,b-6a,b) [L 3 = hydro[tris(3,5-dimethylpyrazol-1-yl)]borato (Tp%, 3), hydro[tris(pyrazol-1-yl)]borato (Tp, 4), cyclopentadienyl (Cp, 5), bis(3,5-dimethylpyrazol-1-yl)acetato (bdmpza, 6); R =SiMe 3 (a), Ph (b)] were prepared in a stepwise fashion from [W(CO) 6 ] and Li[C CR], (CF 3 CO) 2 O and M[L 3 ] (M=Na, K). The formation of 6a,b was highly selective, only complexes with a trans arrangement of the carboxylate group of bdmpza and the alkynylcarbyne ligand were detected. The reaction of [W(CO) 6 ] with Li[C CR], C 2 O 2 Cl 2 and tmeda afforded trans-[Cl(CO) 2 (tmeda)W C C C R] (7a,b). The electron-donating potential of the different tripodal ligands L 3 was studied by IR-and 13 C-NMR spectroscopy and compared to that of the ligand combination Cl/tmeda. The IR data suggest that in these complexes bdmpza is a weaker electron donor than Tp% and Tp but displays stronger electron-donating abilities than Cp. The structures of 6b and 7b were established by X-ray structural analyses.
Polyhedron, 2015
The syntheses and single crystal X-ray structures of the multifunctional acrylamide-derived ligands N-pyrazolyl-2-methylpropanamide (1, = N-ppa Me) and a mixture of 3-and 5-methylpyrazolylpropanamide (2a and 2b, = N-3Me ppa/N-5Me ppa), and their Mn 2+ complexes are reported, as is the Mn 2+ complex of N-triazolylpropanamide (3, = N-tpa). The general synthesis involves treatment of MnCl 2 Á4H 2 O with the appropriate ligand in solution in the presence of triethylorthoformate as dehydrating agent. This way Mn 2 Cl 4 (N-ppa Me) 2 (EtOH) 2 (4), [Mn(N-3Me ppa) 2 (N-5Me ppa)][MnCl 4 ] (5), and MnCl 2 (N-tpa) 2 (EtOH) 2 (6) were obtained. In 4 the N-ppa Me ligand acts as N,O-chelating ligand whose oxygens bridge the two Mn 2+ ions. The ligands are also chelating in 5. In contrast, monodentate N-coordination via the pyrazolyl ring was found for 6. The molecular and crystal structures of 1, 2a, 4, 5, and 6 have been determined by X-ray diffraction. The extensive hydrogen bonding that occurs in these compounds is discussed.
International Journal of Health Sciences (IJHS), 2022
A new ligand 3-(3-acetylthioureido)propanoic acid (ATA) was prepared through the reaction of acetyl chloride, ammonium thiocyanate and -alanine. For this study the following methods were used: FT-IR, 1 H-NMR 13 C-NMR spectra and the Elemental analysis. complexesis of M +2 =Mn,Cu,Ni,Co,Zn,Cd and Hg derived from3-(3acetylthioureido) propanoic acid have been synthesized and characterized by elemental analyses, molar conductance, magnetic suscpility, FT-IR, UV Vis spectra, The results have shown complexation with -alanine derivative with metal ion in a 1:2 ratio. The spectral characterization confirms the formation of ligand and complexes. The evidences from the above results suggest the ligand to be abi dentate ion.
Inorganic Chemistry, 2005
Cl 4 ] with bis(pyrazol-1-yl)methane (bpzm) and bis(pyrazol-1-yl)acetate (Hbpza) and with the lithium salts lithium [bis(3,5-dimethylpyrazol-1-yl)acetate] (Libdmpza) and lithium [bis(3,5-dimethylpyrazol-1-yl)methanesulfonate] (Libdmpzs) produce a series of new compounds containing either a κ 2 -N,N bidentate pyrazolyl ]. X-ray analyses of 1 and 3 show in both cases a distorted octahedral environment around the rhenium atom. The nature and the geometry of the products are strongly determined by the reaction solvent and by the heteroscorpionate ligand itself. When scorpionates bear methylated pyrazolyl rings mixed heterocomplexes Re(O)(bdmpza)(glycol) (11) and Re(O)(bdmpzs)(glycol) (12) are obtained (H 2 glycol ) ethylene glycol). Also 11 shows an octahedral geometry as assessed by X-ray study. Boschi, A.; Uccelli, L.; Tisato, F.; Refosco, F.; Cagnolini, A.; Duatti, A.; Prakash, S.; Bandoli, G.; Vittadini, A. J. Am. Chem. Soc. 2002, 124, 11468-11479. (7) Porchia, M.; Tisato, F.; Refosco, F.; Bolzati, C.; Cavazza-Ceccato, M.; Bandoli, G.; Dolmella A. Inorg. Chem. 2005, in press.
Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 2014
A discrete tetranuclear manganese(II) complex, {(H 3 O) 2 -Mn 4 (4-Haba) 2 (4-aba) 6 (SCN) 4 (H 2 O) 2 ]} (1) and a two-dimensional coordination polymer [Mn(3-aba) 2 ] n (2) (4-Haba = 4aminobenzoic acid, 3-Haba = 3-aminobenzoic acid), have been synthesized and characterized by elemental analyses, IR, X-ray crystallography, and magnetic susceptibility. In complex 1, 4-aba in three types of coordination modes connects Mn II centers to form a discrete tetranuclear anionic molecule. Hydrogen bonding interaction links the tetranu-[a] State Key