Reactions of the aminoiminophenols 2-((2-(dimethylamino)ethylimino)methyl)phenol (HL(1)) or 2-{(3-(dimethylamino)propylimino)methyl}phenol (HL(2)) with nickel(II) chloride, K(2)[PtCl(4)] or copper(II) acetate in alcoholic solution, in the absence or in the presence of sodium azide, afford the corresponding new mononuclear complexes [M(L(1))(X)(H(2)O)(n)] [M = Ni, X = Cl(-), n = 2 (); M = Ni, X = N(3)(-), n = 0 (); M = Pt, X = Cl(-) () or N(3)(-) (), n = 0] or the known dinuclear compound [Cu(L(2))(N(3))](2) (). Complexes , and react with 2-cyanopyridine leading to the [2 + 3] cycloaddition products with 5-(2-pyridyl)tetrazolato [PTZ = N(4)C(2-NC(5)H(4))] ligands [Ni(L(1))(PTZ)](2) (), [Pt(L(1))(PTZ)] () and [Cu(PTZ)(2)(H(2)O)(2)] . The obtained complexes were characterized by IR, (1)H and (13)C (for , and ) NMR spectroscopies, elemental analyses and single crystal X-ray diffraction analyses (for , , , , and ). Complexes and form finite 1D chains and 3D frameworks, respectively, on account of extensive hydrogen bonds involving their coordinated water molecules and the chloride ligand (in the case of ) or tetrazolato nitrogen atoms (in the case of ).

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The [2 + 3] cycloaddition reactions (which are greatly accelerated by microwave irradiation) of the di(azido)platinum(II) compounds cis-[Pt(N(3))(2)(PPh(3))(2)] (1) with cyanopyridines NCR (2) (R = 4-, 3-, and 2-NC(5)H(4)) give the corresponding bis(pyridyltetrazolato) complexes trans-[Pt(N(4)CR)(2)(PPh(3))(2)] (3) [R = 4-NC(5)H(4) (3a), 3-NC(5)H(4) (3b), and 2-NC(5)H(4) (3c)]. Compound 3c has been characterized as the N(1)N(2)-bonded isomer in the solid state by X-ray crystallography and represents the first bis(tetrazolato) complex of this kind. Complexes 3a and 3b have been used as metallaligands to generate heteronuclear coordination polymers in the presence of copper nitrate. A one-dimensional supramolecular architecture was obtained as the exclusive product, {trans-[Pt(2)(N(4)CR)(4)(PPh(3))(4)Cu](n)(NO(3))(2n).nH(2)O (4.nH(2)O) (R = 4-NC(5)H(4)), when 3a was employed, whereas with 3b the heteronuclear square complex trans-[Pt(N(4)CR)(2)(PPh(3))(2)Cu(NO(3))(2)(H(2)O)](2) (5) (R = 3-NC(5)H(4)), composed of Pt/Cu ions, was obtained. All the isolated complexes were characterized by IR, elemental, and (for 3b, 3c, 4, and 5) X-ray structural analyses. Complexes 3 were additionally characterized by (1)H, (13)C, and (31)P {(1)H} NMR spectroscopies.

The [2+3] cycloaddition reaction (which is greatly accelerated by microwave irradiation) of the bis(azido)platinum(II) compound cis‐[Pt(N3)2(PPh3)2] (1) with 4‐cyanobenzaldehyde (2) furnishes the N2N2‐bonded isomer of bis[5‐(4‐formylphenyl)tetrazol‐2‐ate] platinum(II) trans‐[Pt{N4CC6H4(4‐CH=O)}2(PPh3)2] (3a) as the major product, along with the N1N2‐bonded isomer 3b. Treatment of 3a with 2‐dimethylaminoethylamine (4), in refluxing methanol, gives the corresponding N2N2‐bonded bis[(E)‐5‐(4‐{[2‐(dimethylamino)ethylimino]methyl}phenyl)tetrazol‐2‐ate] platinum(II) complex trans‐[Pt{N4CC6H4(4‐CH=NCH2CH2NMe2)}2(PPh3)2] (6) in good yield. An alternative route involves the reaction of 4‐cyanobenzaldehyde (2) with diamine 4 to give the E isomer of 4‐{[2‐(dimethylamino)ethylimino]methyl}benzonitrile N≡CC6H4(4‐CH=NCH2CH2NMe2) (5), followed by the reaction of the latter with bis(azido)platinum(II) complex 1 to afford 6 in similar yield. The reaction of 6 with MCl2 (M = Pd, Ni, Zn, Cu), at room temperature for 3 h regenerates complex 3a as a result of the Schiff base hydrolysis, along with the diamine complex [MCl2(NH2CH2CH2NMe2)] (7). Treatment of 6 with ZnCl2 for 36 h affords a mixture of 3a with its substitution products [Pt{HN4CC6H4(4‐CH=O)}(NH2CH2CH2NMe2)(PPh3)]Cl2 (9; isolated in the tetrazole form) and cis‐[PtCl2(PPh3)2] (10) and diamine complex 7 (M = Zn). The [2+3] cycloaddition reactions of cis‐[Pt(N3)2(PPh3)2] (1) with unsubstituted dicyanobenzenes 11 [1,2‐C6H4(CN)2 (11a), 1,3‐C6H4(CN)2 (11b), 1,4‐C6H4(CN)2 (11c)] occur regioselectively and give the corresponding N2N2‐bonded bis[5‐(cyanophenyl)tetrazol‐2‐ate] trans‐[Pt(N4CC6H4R)2(PPh3)2] complexes 12 (R = 2‐CN 12a, 3‐CN 12b, 4‐CN 12c). The isolated compounds were characterized by IR, 1H NMR, 13C NMR and 31P{1H} NMR (metal complexes) spectroscopy, elemental analyses, ESI‐MS and X‐ray structural analyses (for 3a, 5·HCl, 7, 9 and 12a). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)