The synthesis and structure of new N-(2,6-diisopropylphenyl)-2-phenyldiazenecarboxamide (L2) and N-(2,6-diisopropylphenyl)-2 (perfluorophenyl) diazenecarboxamide (L3) ligands are described. The subsequent reactions of ligands L1, L2 and L3 with trispentafluorophenylboron gave rise to new adducts (A1), (A2) and (A3), where B(C6F5)3 is coordinated to the carbonyl group. New ligands and adducts are characterized by nuclear magnetic resonance (NMR), infrared (IR), and elemental analysis techniques. The crystal structures of all compounds are obtained and described.

The reaction of 3,5-bis(bromomethyl)toluene with benzotriazole yields the bidentate ligand 3,5-bis(benzotriazol-1-ylmethyl)toluene (1). This ligand reacts with [PdCl2(cod)] (cod = 1,5-cyclooctadiene) to give the complex [PdCl2{3,5-bis(benzotriazol-1-ylmethyl)tolyl}] (2). These compounds were characterized by elemental analyses, mass spectra, and FTIR and NMR (¹H, 13C) spectroscopies. The palladium(II) complex 2 shows high activity as catalyst for oxidative amination, involving allyl butyl ether and phthalimide as substrates and PhICl2 as a stoichiometric oxidant.

A reação de 2-bromo-1, 3-bis(bromometil)benzeno com 3, 5-dimetilpirazol e 1H-indazol produz os ligantes tridentados 2-bromo-1, 3-bis(3, 5-dimetilpirazol-1-ilmetil)benzeno (1) e 2-bromo-1, 3-bis(indazol-2-ilmetil)benzeno (2). Estes compostos reagem com [Ni(cod)2] em tetraidrofurano (thf) para formar os complexos de adição oxidativa [NiBr{1, 3-bis(azolilmetil)fenil-N, C, N}], azol = 3, 5-dimetilpirazol (3) e indazol (4), os quais foram isolados em bons rendimentos como sólidos amarelos estáveis e caracterizados por meio de análise elementar, espectroscopia de absorção no infravermelho com transformada de Fourier (FTIR), espectrometria de massa e ressonância magnética nuclear (NMR). Adicionalmente, as estruturas moleculares de 2 e 4 foram determinadas por difratometria de raios X de monocristal. O complexo 4 foi testado como catalisador na reação de polimerização de etileno

The reaction of 2-bromo-1, 3-bis(bromomethyl)benzene with 3, 5-dimethylpyrazole and 1H-indazole yields the tridentate ligands 2-bromo-1, 3-bis(3, 5-dimethylpirazol-1-ylmethyl)benzene (1) and 2-bromo-1, 3-bis(indazol-2-ylmethyl)benzene (2). These compounds react with [Ni(cod)2] in tetrahydrofuran (thf) to form the oxidative addition complexes [NiBr{1, 3-bis(azolylmethyl)phenyl-N, C, N}], azol = 3, 5-dimethylpyrazol (3), indazol (4), which were isolated in good yields as stable yellow solids and characterized by elemental analysis, Fourier-transform infrared spectroscopy (FTIR), mass spectroscopy and nuclear magnetic resonance (NMR). In addition, the molecular structures of 2 and 4 were determined by single-crystal X-ray diffraction analysis. Complex 4 was tested as a catalyst in ethylene polymerization reaction

Reaction of the dinuclear complex [{Ru(CO)3Cl2}J with the Hgand 2-(diphenylphosphineoxide)pyridine (PyPOPh2) in ethanol solution gave the neutral mononuclear complex [Ru(k²-PyPOPh2-N,0)(CO)2Cl2]. The complex was characterized by elemental analysis, IR and RMN spectroscopy, and its molecular structure was determined by single-crystal X-ray diffraction.

Reaction of the chiral compound (S)-(+)-BrCH2CHMeCH2OH with Ph2PK in the presence of lithium diisopropylamide (LDA) and BH3/THF yields the monophosphine (S)-Ph2P(BH3)CH2CHMeCH 2OH(1). The reaction of 1 with ClOSO2Me/Et3N or NaH/MeI gives rise to the formation of the general compound (S)-Ph2P(BH3)CH2CHMeCH 2OR [Cp*IrCl2(PPh2CH2CHMeCH 2OR-P)], which by treatment with pyrrolidine affords (S)-Ph2PCH2CHMeCH2 OR [R = SO2Me (4), Me (6)]. The monophophines 4, 6 and (S)-PPh2CH2CHMeCH2 OH react with [{Cp*IrCl(µ-Cl)}2] to give the neutral compounds [Cp*IrCl2(PPh2CH2CHMeCH 2OR-P)], where only the compound with R = H (7) was fully characterized. Complex 7 reacts with AgBF4 yielding the cationic complex [Cp*IrCl(PPh2CH2CHMeCH2 OH-P,O)]BF4 (8) in which the ligand acts in its bidentate form. Similar synthetic results were obtained using [{Cp*IrI(µ-I)}2] as starting complex .

The electrochemical behavior of binuclear ruthenium(II) complexes of the type [{(arene)RuCl2}2] where arene = benzene (1), toluene (2), p-cymene (3) and hexamethylbenzene, (HMB) (4), have been studied by cyclic voltammetry, coulometry and voltammetry with rotating disk and ring-disk electrodes. These compounds undergo electrochemical quasi-reversible reduction in dimethylsulphoxide (DMSO) and acetonitrile (MeCN). The ruthenium(I) species formed react in a very fast chemical reaction (EC mechanisms), although the rate constants of electrochemical and chemical processes are different for the arenes studied. Conditional rate constants (k) and charge transfer coefficients (a ) for the cathodic reactions were determined by rotating disk techniques, and the kinetic collection efficiency (Nk) was determined with a rotating ring-disk electrode. On the other hand, the binuclear complexes 1 and 2 are quasi-reversibly oxidized in MeCN solution in two electron steps yielding binuclear Ru(III) species, while complex 3 is partially oxidized to give a mixture of products, and complex 4 generates a very unstable species, which chemically returns to the starting reduced complex

Reaction of the dinuclear complex [{(eta5-C5Me5)RhCl} 2(µ-Cl)2] with the chiral phosphine (R)-Ph2PCH2CHMeCH2 OH leads to the complex [{(eta5-C5Me5)RhCl 2(eta¹-Ph2PCH2 CHMeCH2OH-P)](1). This reaction, in the presence of AgBF4, yields the cationic compound [{(eta5-C5Me5)RhCl(eta²- Ph2PCH2CHMeCH2OH-P,O)]BF 4(2). Variable-temperature ¹H NMR and circular dichroism experiments support the stereoselective eta²-chelate coordination of the ligand and the proposed configuration for the metal centre. In a similar way, the reaction of the dimer [{(eta6-C6Me6)RuCl} 2(µ-Cl)2] with the ligands (R)- and (S)-Ph2PCH2CHMeCH2 OH afford the neutral complexes [(eta6-C6Me6)RuCl 2{eta¹-PPh2CH2 CHMeCH2OH-P}] [R-ligand (3), S-ligand (4)], which in turn react with AgBF4 to give the cationic compounds [(eta6-C6Me6)RuCl{eta²-PPh2CH2CHMeCH2 OH-P,O}]BF4 [R-ligand (5), S-ligand (6)]. All complexes have been characterised by elemental analysis, IR and multinuclear NMR spectroscopies

La reacción del complejo dinuclear [{(eta5-C5Me5)RhCl} 2(µ-Cl)2] con la fosfina quiral (R)-Ph2PCH2CHMeCH2 OH conduce a la formación del complejo neutro [{(eta5-C5Me5)RhCl 2(eta¹-Ph2PCH2 CHMeCH2OH-P)](1). Si la reacción se realiza en presencia de AgBF4 se obtiene el complejo catiónico [{(eta5-C5Me5)RhCl(eta²-Ph2PCH2CHMeCH2 OH-P,O)]BF4(2). Experimentos de ¹H NMR a temperatura variable permiten demostrar que la coordinación de tipo quelato de la fosfina es altamente estereoselectiva y medidas de dicroismo circular avalan la configuración propuesta para el centro metálico. De forma similar, la reacción del dímero [{(eta6-C6Me6)RuCl} 2(µ-Cl)2] con los ligandos (R)- y (S)-Ph2PCH2CHMeCH2 OH genera los complejos neutros [(eta6-C6Me6)RuCl 2{eta¹-PPh2CH2 CHMeCH2OH-P}] [(R)- (3), (S)- (4)], los cuales mediante una posterior reacción con AgBF4 forman los compuestos catiónicos [(eta6-C6Me6)RuCl{eta²-PPh2CH2CHMeCH2 OH-P,O}]BF4 [(R)- (5), (S)- (6)]. Todos los complejos han sido caracterizados mediante análisis elemental y espectrocopía IR y de RMN

Reaction of dinuclear complex [{(h6-C6Me6)Ru(µ-Cl)Cl} 2] with the ligand NH(PPh2)2 in 1:2 molar ratio affords the mononuclear complex [(h6-C6Me6)RuCl 2{h1-(PPh2)2NH}](1) which in turn reacts with AgPF6 to yield the cationic compound [(h6-C6Me6)RuCl{h 2-(PPh2)2NH}]PF6 (2). Complex 3 reacts with KOBut to give the neutral complex [(h6-C6Me6)RuCl{h 2-(PPh2)2N}](3). The anionic ligand of complex 3 reacts easily with HBF4 regenerating the starting complex and with MeI by N-methylation of the chelate ligand. The non coordinating P atom of complex 1 reacts with sulfur or selenium to form the P-coordinate monosulphide or selenide ligands, [{(h6-C6Me6)RuCl 2{h1PPh2NHP(E)Ph2 }] (5,6). The treatment of complexes 5 and 6 with AgPF6 affords cationic (7,8) or neutral (9,10) complexes depending of the solvent used. The neutral complex 9 can be N-derivatized by reaction with MeI

La reacción del complejo dinuclear [{(h6-C6Me6)Ru(µ-Cl)Cl} 2] con el ligando NH(PPh2)2 en relación molar 1:2 genera el complejo mononuclear [(h6-C6Me6)RuCl 2{h1-(PPh2)2 NH}](1), el que posteriormente reacciona con AgPF6 formando el complejo catiónico [(h6-C6Me6)RuCl{h 2-(PPh2)2NH}]PF6 (2). El complejo 2 reacciona con KOBut con formación del complejo neutro [(h6-C6Me6)RuCl{h 2-(PPh2)2N}](3). El ligando aniónico del complejo 3 reacciona facilmente con HBF4 regenerando el complejo de partida y con MeI a través de la metilación del átomo de nitrógeno del ligando coordinado. El átomo de fósforo no coordinado del complejo 1 reacciona con azufre o selenio con formación del ligando coordinado monosustituído,[{(h6-C6 Me6)RuCl2{h1PPh 2NHP(E)Ph2}] (5,6). El tratamiento de los complejos 5 y 6 con AgPF6 conduce a la formación de compuestos catiónicos (7,8) o neutros (9,10) dependiendo del tipo de disolvente utilizado. El atomo de nitrógeno del complejo neutro 9 puede ser derivatizado por reacción con MeI

The complexes <FONT FACE=Symbol>[ Pt{(P(O)(OMe)2)2H}2]</FONT> and <FONT FACE=Symbol>[ PtCl(PPh3){(P(O)(OMe)2) 2H}]</FONT> react with Tl(acac) in chloroform or with KOH in methanol solution to yield thetrinuclear and binuclear complexes, <FONT FACE=Symbol>[ Pt{m -P)O)(OMe)2}4M2]</FONT> and <FONT FACE=Symbol>[ PtCl(PPh3){m -P(O)(OMe)2 }2M]</FONT> (M = Tl, K), respectively. These derivatives react with (PtMe3)2SO4· 4H2O or <FONT FACE=Symbol>[ {Me3PtI}4]</FONT> with formation of the solvated complexes <FONT FACE=Symbol>[ Pt{m -P(O))OMe)2}4{PtMe 3(MeOH)}2]</FONT> and <FONT FACE=Symbol>[ PtCl(PPh3){m -P(O)(OMe)2 }2{PtMe3(MeOH)}]</FONT> .Addition of donor ligands displaces the coordinated methanol to afford the corresponding adducts <FONT FACE=Symbol>[ Pt{m -P(O)(OMe)2}4{PtMe3L}2]</FONT> (L = py, 3,5-Me2py, P(p-MeOPh)3}and <FONT FACE=Symbol>[ PtCl(PPh3){m -P(O)(OMe)2 }2{PtMe3L}]</FONT> (L = py, PPh3). The complexes are characterized by elemental analysis, and IR and NMR spectroscopy

Los complejos Pt{(P(O)(OMe)2)2H}2 ] y <FONT FACE=Symbol>[ PtCl(PPh3){(P(O)(OMe)2) 2H}]</FONT> reaccionan con Tl(acac) en disolución de cloroformo o con KOH en metanol generando los compuestos trinucleares y dinucleares, Pt{my -P)O)(OMe)2}4M2] y<FONT FACE=Symbol>[ PtCl(PPh3){m -P(O)(OMe)2 }2M]</FONT> (M = Tl, K), respectivamente. Estos derivados reaccionan con (PtMe3)2SO4· 4H2O o <FONT FACE=Symbol>[{Me3PtI}4]</FONT> con formación de las especies solvatadas <FONT FACE=Symbol>[ Pt{m -P(O))OMe)2}4{PtMe3(MeOH)}2]</FONT> y <FONT FACE=Symbol>[ PtCl(PPh3){m -P(O)(OMe)2}2{PtMe3(MeOH)}]</FONT> . La adición de ligandos dadores producen el desplazamiento del metanol coordinado formando los correspondientes aductos <FONT FACE=Symbol>[Pt{m -P(O)(OMe)2}4{PtMe 3L}2]</FONT> (L = py, 3,5-Me2py, P(p-MeOPh)3} y<FONT FACE=Symbol>[PtCl(PPh3){m -P(O)(OMe)2}2{PtMe3L}]</FONT> (L = py, PPh3). Los complejos obtenidos fueron caracterizados mediante análisis elemental y espectroscopías IR y de RMN