S-, O-, O,O′- p-toluenesulfinato complexes of iron(II), cobalt(II) and nickel(II) with polydentate tripod-like phosphines,crystal structure of 1,1,1-tris(diphenylphosphinomethyl)ethane p-toluenesulfinatocobalt(II) perchlorate

Reaction of sodium p-toluenesulfinate with iron(II), cobalt(II) and nickel(II) aquo ions in the presence of the poly(tertiary phosphines) 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos), tris(2-diphenylphosphinoethyl)amine (np₃) and tris(2-diphenylphosphinoethyl)phosphine (pp₃) gives five-coordinated p-toluenesulfinato complexes of formulae [(triphos)Co(p-tolSO₂)]ClO₄ and [LM(p-tolSO₂)]BPh₄ (L = pp₃, M = Fe, Co, Ni; L = np₃, M = Co, Ni). The nickel derivatives are diamagnetic with the p-toluenesulfinate ligand bonded to the metal through the sulfur atom. The iron and cobalt complexes are paramagnetic, low or high spin, with the _p-toluenesulfinate ion linked to the metal via one oxygen (np₃ and pp₃ derivatives) or both oxygen atoms (cobalt-triphosderivative).The structure of [(triphos)Co(p-tolSO₂)]ClO₄ has been determined from three-dimensional X-ray data collected by counter methods. The crystals are monoclinic, space group P2₁/n with a = 20.942(9), b =, 9.652(4), c= 22.040(8), Å, β, = 96.86(5)°, d_c = 1.407 gcm^?3 for Z = 4. Full-matrix least-squares refinements converged at the conventional R factor of 0.063 for 5573 observed reflections. The complex cation has a distorted square pyramidal geometry with the sulfinate group acting as a bidentate ligand through the two oxygen atoms.     

Phosphorus and Arsenic Chalcogenides as Reagents Toward Transition Metal-Ligand Systems

Abstract

The compounds obtained by reacting the P₄S₃, P₄Se₃ and As₄S₃ cage molecules with various transition metal-ligand moieties are reported. The transition metal-ligand systems are bound either to the intact molecules or to fragments (hexa- or tri-atomic) originating from the cage molecules. Such compounds provide examples of selective activation of cage molecules by metal moieties.     

Three-dimensional molecular reconstruction of rat heart with mass spectrometry imaging

Cardiovascular diseases are the world’s number one cause of death, accounting for 17.1 million deaths a year. New high-resolution molecular and structural imaging strategies are needed to understand underlying pathophysiological mechanism. The aim of our study is (1) to provide a molecular basis of the heart animal model through the local identification of biomolecules by mass spectrometry imaging (MSI) (three-dimensional (3D) molecular reconstruction), (2) to perform a cross-species validation of secondary ion mass spectrometry (SIMS)-based cardiovascular molecular imaging, and (3) to demonstrate potential clinical relevance by the application of this innovative methodology to human heart specimens. We investigated a MSI approach using SIMS on the major areas of a rat and mouse heart: the pericardium, the myocardium, the endocardium, valves, and the great vessels. While several structures of the heart can be observed in individual two-dimensional sections analyzed by metal-assisted SIMS imaging, a full view of these structures in the total heart volume can be achieved only through the construction of the 3D heart model. The images of 3D reconstruction of the rat heart show a highly complementary localization between Na⁺, K⁺, and two ions at m/z 145 and 667. Principal component analysis of the MSI data clearly identified different morphology of the heart by their distinct correlated molecular signatures. The results reported here represent the first 3D molecular reconstruction of rat heart by SIMS imaging.