Binuclear Hydridoplatinum(II): One‐Pot Synthesis, INS Spectra and X‐ray Crystal Structure of [Pt₂(dcype)₂(H)₃][BPh₄] {dcype = 1,2‐Bis(dicyclohexylphosphanyl)ethane}

Abstract

The binuclear platinum (II)

Reaction Chemistry of Complexes Containing PtH, PtSH, or PtS Fragments: From Their Apparent Simplicity to the Maze of Reactions Underlying Their Interconversion

“…[14] The calculated PtÀH frequencies fully agree with the ascription of a type C structure to 1 t. For the Pt À H stretching vibration that involves the non-bridging hydrides H1 and H2 two frequencies at 2119 cm À1 (Pt1 À H1) and 1996 cm À1 (Pt2 À H2) are obtained. The symmetric and anti-symmetric Pt-H3-Pt vibrational modes appear at 1240 and 1529 cm À1 , respectively.…”

“…Complex 1 was synthesized in high yields by using a onepot reaction procedure that involves the mixing of [PtCl 2 - The synthetic procedure we followed to obtain 1 has already been reported for the [Pt 2 (H) 3 A C H T U N G T R E N N U N G (dcype) 2 ]X (dcype = 1,2-bis(dicyclohexylphosphanyl)-ethane; X = BF 4 , Cl, OH, and BPh 4 ) analogues, [14] and affords much better yields than the two synthetic alternatives used to obtain [Pt 2 (H) 3 A C H T U N G T R E N N U N G (dppp) 2 ]BF 4 , [15] which includes the same diphosphane ligand as 1. Addition of the sodium salts of BF 4 À , BPh 4 À , or PF 6 À instead of ClO 4 À led us to unsatisfactory yields, and that of Cl À reversed the reaction by causing formation of the starting complex [PtCl 2 A C H T U N G T R E N N U N G (dppp)].…”

“…[14] The different disposition of the H ligands around the Pt centers in structures B and C causes remarkable differences in the vibrational spectra. The stretching frequency for a terminal Pt À H group is expected to be in the region of 1900-2100 cm À1 , while the modes involving the m-bridging H may be described in terms of symmetric and antisymmetric M-H-M stretching modes in the region of 1000-1400 cm…”

“…[14] As described in this work, the X-ray diffraction of 1 made it possible to determine the structure of this complex, including the direct location of the hydrogen atoms. Overall, the structure of 1 is consistent with that reported in neutron diffraction studies for its dppe-containing analogue.…”

“…Before commenting on the theoretical result, we should stress that factors such as the bite angle of the chelating ligands, the steric demand of the substituents on the phosphorous atoms and even more subtle factors such as crystal-packing forces could be responsible for the existence of different structures. [14] Calculations have been performed in a simplified model (dhpp instead of the actual dppp) in gas phase, which therefore does not consider the full subtlety of real systems. However, a joint analysis of the structural and energetic theoretical results and comparison with the experimental results can help to describe the bonding scheme on [Pt 2 (H) 3 …”