Pentacoordinate [PtCl2(η2-C2H4)(N–N′)] complexes with asymmetrically hindered nitrogen donor chelates. Stereospecific synthesis of syn- and anti-[PtCl(η1-CH2CH2OMe)(Mebpy)]

Photoinduced Biphasic Hydrogen Evolution: Decamethylosmocene as a Light‐Driven Electron Donor

“…Synthesis of Complexes: Complexes [PtCl 2 (η 2 ‐CH 2 =CH 2 )(Me 4 en)] ( Me 4 1 ),30 [PtCl 2 (η 2 ‐CH 2 =CH 2 )(bpy)] ( 3 ),10,39 [PtCl 2 (η 2 ‐CH 2 =CH 2 )(Mebpy)] ( Me3 ),10 [PtCl 2 (η 2 ‐CH 2 =CH 2 )(phen)] ( 4 ),10 and [PtCl 2 (η 2 ‐CH 2 =CH 2 )(Me 2 phen)] ( Me 2 4 ),16,20 were synthesized by reported methods (for these complexes, only additional here discussed new NMR spectroscopic data, collected at 263 K, are reported in the Supporting Information). The new pentacoordinate complexes, discussed in this work, were synthesized by an extension of previously reported methods.…”

Hindrance, Donor Ability of Men∩NN Chelates and Overall Stability of Pentacoordinate [PtCl2(η2‐CH2=CH2)(Men∩NN)] Complexes as Observed by η2‐Olefin 1JPt,C Modulation: An NMR Study

“…Elemental analyses were performed with a CHN Eurovector EA 3011. [30] [PtCl 2 (η 2 -CH 2 =CH 2 )(bpy)] (3), [10,39] [PtCl 2 (η 2 -CH 2 =CH 2 )(Mebpy)] (Me3), [10] [PtCl 2 (η 2 -CH 2 =CH 2 )(phen)] (4), [10] and [PtCl 2 (η 2 -CH 2 =CH 2 )(Me 2 phen)] (Me 2 4), [16,20] were synthesized by reported methods (for these complexes, only additional here discussed new NMR spectroscopic data, collected at 263 K, are reported in the Supporting Information). The new pentacoordinate complexes, discussed in this work, were synthesized by an extension of previously reported methods.…”

“…[35][36][37] In previous work, the requirements that determine thermodynamic stability of such pentacoordinate complexes were clearly underlined. [10,20,29,[38][39][40][41] The increase of both the _ NN chelate steric hindrance and the π-acceptor ability of the olefins seems to increase the thermodynamic stability of pentacoordinate complexes. [34,38] On the other hand, a moderate steric hindrance of the axial ligands also seems to generally stabilize pentacoordination, with respect to the square-planar species obtained after loss of the η 2 -olefin or an axial ligand.…”

Square‐Planar PtII versus Octahedral PtIV Halido Complexes: 195Pt NMR Explained by a Simple Empirical Approach

“…We recently reported the existence of specific linear relationships between the number and orientation of alkyl groups bonded to coordinated dinitrogen ligands and the observed 195 Pt NMR frequency for pentacoordinate and square‐planar Pt II species , . To better understand the relationship between the observed NMR chemical shifts and the molecular structures of platinum complexes, we studied the Pt II pentacoordinate complexes of the type [PtXY(η 2 ‐olefin)(N^N)] and [PtXY(η 2 ‐alkyne)(N^N)] (X,Y = Cl, Br, I; N^N = dinitrogen ligand). In particular, collection of the 1 H, 13 C, 15 N, and 195 Pt NMR spectroscopic data of the considered pentacoordinate complexes allowed the linear correlation of the chemical shift frequencies with both the spatial disposition of the observed nuclei and the ionic radii of the apical halido ligands (Figure , A) , .…”