Crystal structure and magnetic study of the complex salt [RuCp(PTA)2-µ-CN-1κC:2κN-RuCp(PTA)2][Re(NO)Br4(EtOH)0.5(MeOH)0.5].

A new RuII-ReII complex salt, µ-cyanido-κ2 C:N-bis-[(η5-cyclo-penta-dien-yl)bis(3,5,7-tri-aza-phosphaadamantane-κP)ruthenium(II)] tetra-bromido-(ethanol/methanol-κO)nitrosylrhenate(II), [Ru(CN)(C5H5)2(C6H12N3P)4][ReBr4(NO)(CH4O)0.5(C2H6O)0.5] or [RuCp(PTA)2-µ-CN-1κC:2κ2 N-RuCp(PTA)2][Re(NO)Br4(EtOH)0.5(MeOH)0.5] (PTA = 3,5,7-tri-aza-phosphaadaman-tane) was obtained and characterized by single-crystal X-ray diffraction, elemental analysis and infrared spectroscopy. The title salt was obtained by liquid-liquid diffusion of methanol/DMSO solutions of (NBu4)[Re(NO)Br4(EtOH)] and [(PTA)2CpRu-µ-CN-1κC:2κ2 N-RuCp(PTA)2](CF3SO3). The RuII and ReII independent moieties correspond to a binuclear and mononuclear complex ion, respectively. A deep geometrical parameter analysis was performed, and no significant differences were found with earlier reports containing similar mol-ecules. The magnetic properties were investigated in the temperature range 2.0-300 K, and the complex behaves as a quasi-magnetically isolated spin doublet with weak anti-ferromagnetic inter-actions.

The crystal structure and magnetic properties of 3-pyridinecarboxylate-bridged Re(II)M(II) complexes (M = Cu, Ni, Co and Mn).

The novel Re(II) complex NBu4[Re(NO)Br4(Hnic)] (1) and the heterodinuclear compounds [Re(NO)Br4(µ-nic)Ni(dmphen)2]·½CH3CN (2), [Re(NO)Br4(µ-nic)Co(dmphen)2]·½MeOH (3), [Re(NO)Br4(µ-nic)Mn(dmphen)(H2O)2]·dmphen (4), [Re(NO)Br4(µ-nic)Cu(bipy)2] (5) [Re(NO)Br4(µ-nic)Cu(dmphen)2] (5') (NBu4(+) = tetra-n-butylammonium cation, Hnic = 3-pyridinecarboxylic acid, dmphen = 2,9-dimethyl-1,10-phenanthroline, bipy = 2,2'-bipyridine) have been prepared and the structures of 1-5 determined using single crystal X-ray diffraction. The structure of 1 consists of [Re(NO)Br4(Hnic)](-) anions and NBu4(+) cations. Each Re(II) is six-coordinate with four bromide ligands, a linear nitrosyl group and a nitrogen atom from the Hnic molecule, in a distorted octahedral surrounding. The structures of 2-5 are made up of discrete heterodinuclear Re(II)M(II) units where the fully deprotonated [Re(NO)Br4(nic)](2-) entity acts as a didentate ligand through the carboxylate group towards the [Ni(dmphen)2](2+) (2), [Co(dmphen)2](2+) (3), [Mn(dmphen)(H2O)2](2+) (4) and [Cu(bipy)2](2+) (5) fragments, the Re-M separation across the nic bridge being 7.8736(8) (2), 7.9632(10) (3), 7.7600(6) (4) and 8.2148(7) Å (5). The environment of the Re(II) ion in 2-5 is the same as 1 that in and all M(II) are six-coordinate in highly distorted octahedral surroundings, the main source of the distortion being due to the reduced bite of the chelating carboxylate. The magnetic properties of 1-5' were investigated in the temperature range 1.9-300 K. 1 behaves as a quasi-magnetically isolated spin doublet with very weak antiferromagnetic interactions through space Br···Br contacts. Its magnetic susceptibility data were successfully modeled through a deep analysis of the influence of the ligand field, spin-orbit coupling, tetragonal distortion and covalence effects as variable parameters. Compounds 2-5' exhibit weak antiferromagnetic interactions. The intramolecular exchange pathway in this family being discarded because of the symmetry of magnetic orbitals of the Re(II) ion (d(xy)) precludes any spin delocalization on the bridging nic orbitals, the observed magnetic interactions are most likely mediated by π-π type interactions between the peripheral ligands which occur in them. Only in the case of 4, short through space Br···Br contacts of ca. 4.03 Å (values larger than 5.5 Å in 2, 3 and 5) could be involved in the exchange coupling.

Synthesis, crystal structure and magnetic properties of the Re(II) complexes NBu4[Re(NO)Br4(L)] (L = pyridine and diazine type ligands).

Four novel Re(II) complexes of formula NBu4[Re(NO)Br4(L)] [NBu4(+) = tetra-n-butylammonium cation and L = pyridine (1), pyrazine (2), pyrimidine (3), pyridazine (4)] have been prepared by a substitution reaction involving NBu4[Re(NO)Br4(EtOH)] and L. Their crystal structures have been determined by single crystal X-ray diffraction. They are all mononuclear complexes whose structure is made up of [Re(NO)Br4L](-) anions and NBu4(+) cations. Each Re(II) ion is six-coordinate with four bromide ligands, a linear nitrosyl group and one monodentate nitrogen donor L building a tetragonally distorted octahedral surrounding. The Re-Br bond distances cover a narrow range [2.5048(8)-2.5333(5) Å] and they are longer than the Re-NO [1.688(15)-1.736(3) Å] and Re-N bonds [2.219(4)-2.234(3) Å]. The magnetic properties of 1-4 have been investigated in the temperature range 1.9-295 K. They behave like quasi magnetically isolated spin doublets with very weak antiferromagnetic interactions through intermolecular BrBr contacts. Their magnetic properties are discussed through a deep analysis of the influence of the ligand field, spin-orbit coupling, tetragonal distortion and covalence effects. The values of the temperature-independent paramagnetism for 1-4 are also substantiated and compared to those previously reported in related systems.

Magneto-structural studies on heterobimetallic malonate-bridged M(II)Re(IV) complexes (M = Mn, Co, Ni and Cu).

The mononuclear Re(IV) compound of formula (PPh(4))(2)[ReBr(4)(mal)] (1) was used as a ligand to obtain the heterobimetallic species [ReBr(4)(µ-mal)Co(dmphen)(2)]· MeCN (2), [ReBr(4)(µ-mal)Ni(dmphen)(2)] (3), [ReBr(4)(µ-mal)Mn(dmphen)(2)] (4a), [ReBr(4)(µ-mal)Mn(dmphen)(H(2)O)(2)]·dmphen·MeCN·H(2)O (4b), [ReBr(4)(µ-mal)Cu(phen)(2)]·1/4H(2)O (5) and [ReBr(4)(µ-mal)Cu(bipy)(2)] (6) (mal = malonate dianion, dmphen = 2,9-dimethyl-1,10-phenanthroline, phen = 1,10-phenanthroline and bipy = 2,2'-bipyridine). The structures of 2 and 5 (single-crystal X-ray diffraction) are made up of neutral [ReBr(4)(µ-mal)M(AA)] dinuclear units [AA = dmphen with M = Co (2) and AA = phen with M = Cu (5)] where the metal ions are connected through a malonate ligand which exhibits simultaneously the bidentate [at the Re(IV)] and monodentate [at the M(II)] coordination modes. The carboxylate-malonate group in them adopts the anti-syn conformation with intramolecular ReM separation of 5.098(8) (2) and 4.947(2) Å (5). The magnetic properties of 1-6 were investigated in the temperature range 1.9-295 K. The magnetic behaviour of 1 is the expected for a magnetically isolated Re(IV) complex with a large value of the zero-field splitting (2D ca. -70 cm(-1)) whereas weak antiferromagnetic interactions between Re(IV) and M(II) are observed in the heterobimetallic compounds 2 (J = -0.63 cm(-1)), 3 (J = -1.37 cm(-1)), 4a (J = -1.29 cm(-1)), 5 (J = -1.83 cm(-1)) and 6 (J = -0.26 cm(-1)). Remarkably, 4b behaves as a ferrimagnetic chain with regular alternating Re(IV) and Mn(II) cations (J = -2.64 cm(-1)).

Magnetic properties and molecular structures of binuclear (2-pyrazinecarboxylate)-bridged complexes containing Re(IV) and M(II) (M = Co, Ni).

Three novel Re(iv) compounds, the mononuclear complex Bu(4)N[ReBr(5)(Hpyzc)] (1) and the heterobimetallic complexes [ReBr(5)(mu-pyzc)M(dmphen)(2)].2CH(3)CN [M = Co (2), Ni (3)] (Hpyzc = 2-pyrazinecarboxylic acid, dmphen = 2,9-dimethyl-1,10-phenanthroline), have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. The structure of 1 consists of [ReBr(5)(Hpyzc)](-) complex anions and tetrabutylammonium cations, Bu(4)N(+). The Re(iv) is surrounded by five bromide anions and a N-donor Hpyzc monodentate ligand, in a distorted octahedral environment. The structures of 2 and 3 consist of dinuclear units [ReBr(5)(mu-pyzc)M(dmphen)(2)], with the metal ions linked by a pyzc bridge ligand, being bidentate toward M(II) and monodentate toward Re(IV). The environment of Re(IV) is the same as in 1, whereas M(II) is six-coordinate, being surrounded by four nitrogen atoms of two bidentate dmphen ligands and one oxygen atom and one nitrogen atom of the pyzc anion. The magnetic properties of 1-3 were investigated in the temperature range 2.0-300 K. 1 shows the expected magnetic behavior for a mononuclear Re(IV) complex with a weak intermolecular antiferromagnetic coupling at low temperatures. The bimetallic complexes exhibit an intramolecular ferromagnetic coupling between Re(IV) and the M(II) ion (Co, Ni).

Synthesis, crystal structure and magnetic properties of novel heterobimetallic malonate-bridged MIIReIV complexes (M = Mn, Fe, Co and Ni).

Five novel ReIV-MII bimetallic complexes of formula [ReCl4(mu-mal)M(dmphen)2].MeCN [M = Co (1), Fe (2) and Ni (3)], [ReCl4(mu-mal)Ni(dmphen)(MeCN)2(H2O)].(MeCN)0.5(H2O)0.5 (4), and [ReCl4(mu-mal)Mn(dmphen)(H2O)2].dmphen.MeCN.H2O (5) (mal = malonate dianion, dmphen = 2,9-dimethyl-1,10-phenanthroline) have been synthesized, and the structures of 1, 2, 4, and 5 determined by single-crystal X-ray diffraction. The structures of 1 and 2 consist of neutral [ReCl4(mu-mal)M(dmphen)2] dinuclear units where the metal ions are linked through a malonate ligand which adopts simultaneously the bidentate (at ReIV) and monodentate (at MII) coordination modes. The bridging carboxylate-malonate group in them exhibits the anti-syn conformation. The rhenium atom is six-coordinated with four chloro atoms and two carboxylate-oxygens from a bidentate malonate group in a distorted octahedral environment. The M atom is five-coordinated being surrounded by four nitrogen atoms of two bidentate dmphen ligands and one oxygen atom of the malonato ligand. There are also ReIV(mu-mal)NiII dinuclear units in 4 with the same type of bridge, but the nickel atom is six-coordinated with one bidentate dmphen, two molecules of acetonitrile and one water molecule as peripheral ligands. Compound 5 is a neutral chain compound with regular alternating rhenium(IV) and manganese(II) ions. The [ReCl4(mal)]2- units in each chain act as bismonodenate ligands through two carboxylate-oxygen atoms toward [Mn(dmphen)(H2O)2]2+ entities. Variable-temperature magnetic measurements of 1-5 in the temperature range 2.0-300 K show the occurrence of weak antiferromagnetic interactions which are rationalized on the basis of the structural knowledge and simple orbital considerations. Very noticeable is compound 5, a ferrimagnetic chain with regular alternating ReIV and MnII cations.

Rhenium(IV)-copper(II) heterobimetallic complexes with a bridge malonato ligand. Synthesis, crystal structure, and magnetic properties.

The Re(IV) complex [ReCl4(mal)]2-, in the form of two slightly different salts, (AsPh4)1.5(HNEt3)0.5[ReCl4(mal)] (1a) and (AsPh4)(HNEt3)[ReCl4(mal)] (1b), and the Re(IV)-Cu(II) bimetallic complexes [ReCl4(mu-mal)Cu(phen)2].CH3CN (2), [ReCl4(mu-mal)Cu(bpy)2] (3), and [ReCl4(mu-mal)Cu(terpy)] (4) (mal=malonate dianion, AsPh4=tetraphenylarsonium cation, HNEt3=triethylammonium cation, phen=1,10-phenanthroline, bpy=2,2'-bipyridine and terpy=2,2':6',2' '-terpyridine) have been synthesized and the structures of 1a, 1b, 2, and 3 determined by single-crystal X-ray diffraction. The structures of 1a and 1b are made up of discrete [ReCl4(mal)]2- anions and AsPh4+ and HNEt3+ cations, held together by electrostatic forces and hydrogen bonds. The Re(IV) atom is surrounded by four chloride anions and a bidentate malonate group, in a distorted octahedral environment. The structure of 2 consist of neutral dinuclear units [ReCl4(mu-mal)Cu(phen)2], with the metal ions united through a bridge carboxilato. The environment of Re(IV) is nearly identical to that in the mononuclear complex, and Cu(II) is five coordinate, being surrounded by four nitrogen atoms of two bidentate phen ligands and one oxygen atom of the malonato ligand. In 3, there are also dinuclear units, [ReCl4(mu-mal)Cu(bpy)2], but the Cu(II) ions complete a distorted octahedral coordination by binding with the free malonato oxygen atom of a neighbor unit, resulting in an infinite chain. The magnetic properties of 1-4 were also investigated in the temperature range 2.0-300 K. The magnetic behavior of 1a and 1b is as expected for a Re(IV) complex with a large value of the zero-field splitting (2D ca. 110 cm(-1)). For the bimetallic complexes, the magnetic coupling between Re(IV) and Cu(II) is antiferromagnetic in 2 (J=-0.39 cm(-1)), ferromagnetic in 4 (J=+1.51 cm(-1)), and nearly negligible in 3 (J=-0.09 cm(-1)).