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Linear Triplatinum Tetrahydride Complex Supported by Triphosphine Ligands, [Pt 3 (µ‐H) 2 (H) 2 (µ‐dpmp) 2 ](BF 4 ) 2 {dpmp = bis(diphenylphosphinomethyl)phenylphosphine}
Author(s) -
Tanase Tomoaki,
Yamamoto Kana,
Hatano Rika,
Nakamae Kanako,
Kure Bunsho,
Ura Yasuyuki,
Nakajima Takayuki
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201601505
Subject(s) - chemistry , protonation , nuclear magnetic resonance spectroscopy , hydride , spectroscopy , crystallography , phenylphosphine , stereochemistry , hydrogen , physics , catalysis , organic chemistry , ion , quantum mechanics , phosphine
By treating [Pt 6 (µ‐H)(H) 2 (µ‐dpmp) 4 ]BH 4 [ 4 , dpmp = bis(diphenylphosphinomethyl)phenylphosphine] with an excess amount of HBF 4 in N , N ‐dimethylformamide (DMF), a triplatinum tetrahydride complex, [Pt 3 (µ‐H) 2 (H) 2 (µ‐dpmp) 2 ](BF 4 ) 2 ( 5 ), was obtained in 51 % yield and was characterized by IR, UV/Vis, 1 H NMR, and 31 P{ 1 H} NMR spectroscopy in addition to ESI mass spectrometry, X‐ray crystallography, and DFT calculations. Complex 5 is composed of linear trinuclear platinum centers supported by two dpmp ligands, {Pt 3 (µ‐dpmp) 2 } 6+ , which accommodate two terminal and two bridging hydrides in a HPtHPtHPtH zigzag structure. The hydride positions were determined by DFT optimization with B3LYP/GD3BJ functionals. Variable‐temperature 1 H{ 31 P} NMR spectroscopy in [D 7 ]DMF revealed that the bridging hydrides exhibit fluxional behavior and migrate along the Pt 3 chain by switching the bridging site, whereas the terminal hydrides are not exchanged with the bridging ones. The present results suggest that the divalent linear triplatinum unit of {Pt 3 (µ‐dpmp) 2 } 2+ (Pt 3 II ), which is a building block to construct [Pt 6 (µ‐H)(H) 2 (µ‐dpmp) 4 ] + ( 4 , Pt 3 II Pt 3 II ), formally acts as a four‐electron source to result in [Pt 3 (µ‐H) 2 (H) 2 (µ‐dpmp) 2 ] 2+ ( 5 , Pt 3 VI ) through protonation.