Noé Zúñiga-Villarreal

Synthesis, spectroscopic characterization and crystal and molecular structure of tetrakis(carbonyl)(tetraphenyldithioimidodiphosphinato) manganese(I), Mn(CO)4[(SPPh2)2N]

Abstract Mn(CO) 4 [(SPPh 2 ) 2 N] was prepared by allowing [Mn(CO) 5 ]Br to react with K[SPPh 2 ) 2 N], in THF. The compound was characterized by IR, mass and NMR ( 1 H, 13 C, 31 P) spectroscopy, and its crystal and molecular structure was determined by single-crystal X-ray diffraction. The lattice contains two independent, monomeric molecules, ( 1 ) and ( 1a ). The metal atom has a distorted octahedral coordination geometry (C ax MnC ax 175.9(3)° in ( 1 ), 176.9(3)° in ( 1a )), with two carbonyl groups and the two sulfur atoms of the symmetric monometallic bidentate (mean PS 2.021(2) A in ( 1 ), 2.020(2) A in ( 1a )) dithio ligand unit in equatorial positions (mean MnS 2.420(2), MnC eq 1.804(4), MnC ax 1.855(5) A in ( 1 ), MnS 2.417(2), MnC eq (2) MnC ax 1.862(5) A in ( 1a )). The main difference between the two independent molecules is the conformation of the inorganic MnS 2 P 2 N chelate ring.

A mixed-valence dimanganese complex synthesized from the [Ph2P(O)NP(O)Ph2]− anion with [BrMn(CO)5]

Abstract The reaction of the [Ph2P(O)NP(O)Ph2]− anion with [BrMn(CO)5] in refluxed dichloromethane afforded the mixed-valence complex [Mn2(CO)3{Ph2P(O)NP(O)Ph2-μ-O,O′}3] (1). The single-crystal X-ray analysis of 1 shows that its overall geometry can be regarded as confacial octahedral–trigonal prismatic. The six-membered MnO2P2N rings adopt a twisted-boat conformation. Although the distance between the metal centers, 3.160 A, is rather short, we discard a formal bonding interaction since the fragment Mn(CO)3 fulfills the 18e− rule with coordination to two oxygen atoms and a covalent interaction with a third oxygen atom.

A new ligating mode for the anions of the type [R2P(S)NP(S)R2]−: study of the interaction of [K{Me2P(S)NP(S)Me2}] with the early transition halometalcarbonyl, [BrMn(CO)5]

Abstract The thermal reaction of [BrMn(CO)5] with [K{Me2P(S)NP(S)Me2}] afforded the dinuclear complex [Mn2(CO)6{Me2P(S)NP(S)Me2-μ-S,S′}2] (1). The single-crystal X-ray analysis of 1 shows that this complex is formed by three fused cycles: one four-membered ring and two six-membered rings. The latter show a pseudochair conformation with the Mn and N atoms at the apices. There are two molecules, 1 and 1a, in the unit cell crystallographically independent with identical conformation.

Hydrogen and oxygen activation by an iridium precursor containing the 4,5-bis(diphenylthiophosphinoyl)-1,2,3-triazolate ligand

The novel mononuclear complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(coe)2] was prepared starting from the dimer [Ir(coe)2(μ-Cl)]2 (coe = cyclooctene) and potassium 4,5-bis(diphenylthiophosphinoyl)-1,2,3-triazolate, K[4,5-(P(S)Ph2)2Tz]. Reaction of [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(coe)2] with two equivalents of PPh3 led to complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(PPh3)2]; which, upon exposure to atmospheric air at room temperature, fixed molecular oxygen to produce complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(PPh3)2O2]. Molecular hydrogen also added oxidatively to complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(PPh3)2] to form the Ir(III) dihydride complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(PPh3)2(H)2]. Carbon–hydrogen bond activation was effected when complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(coe)2] was made to react with triphenylphosphite to give the ortho-metallated complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(P(OC6H4)(OPh)2)(P(P(OPh)3)(H)]. The new compounds were characterized by spectroscopic methods and, excepting for [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(PPh3)2], by single crystal X-ray analysis. Oxygen and hydrogen activation by the diphosphane complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(PPh3)2] compared with the inertness of the diolefin complex [Ir(κ2-S,N-(4,5-(P(S)Ph2)2Tz))(coe)2] to such processes was assessed by means of a DFT-QTAIM analysis.