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Photochemical Synthesis of cis , trans , cis ‐1,2,3,4‐Tetrakis(diphenylphosphanyl)buta‐1,3‐diene and Its Metal Coordination
Author(s) -
Prock Johannes,
Ehrmann Katharina,
Viertl Wolfgang,
Pehn Richard,
Pann Johann,
Roithmeyer Helena,
Bendig Marvin,
Rodríguez Villalón Alba,
Kopacka Holger,
Dumfort Alexander,
Oberhauser Werner,
Clausing Simon T.,
Knör Günther,
Brüggeller Peter
Publication year - 2018
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.201800804
Subject(s) - chemistry , intramolecular force , dimer , cycloaddition , diene , acetylene , crystal structure , denticity , metal , stereochemistry , photochemistry , medicinal chemistry , crystallography , catalysis , organic chemistry , natural rubber
The new bis(bidentate) tetraphosphane cis , trans , cis ‐1,2,3,4‐tetrakis(diphenylphosphanyl)buta‐1,3‐diene (dppbd) ( 7 ) was obtained by applying a photochemical synthetic protocol. The key step of the photochemical reaction consisted of an intramolecular [2+2] cycloaddition involving a C–C double and triple bond of the Pt‐dimer species of the formula [Pt 2 Cl 4 (dppa)( trans ‐dppen)] ( 2 ) {dppa = 1,2‐bis(diphenylphosphanyl)acetylene and dppen = 1,2‐bis(diphenylphosphanyl)ethene} leading to [Pt 2 Cl 4 (dppbd)] ( 5 ). The asymmetrically bridged precursor complex 2 was obtained by combinatorial chemistry. Single crystal X‐ray structure analyses of 2 and 5 proved that the intramolecular photochemical reaction occurred. Cyanolysis of 5 gave 7 , which was oxidized to dppbdO4 ( 8 ). Compounds 7 , 8 , and the Pd II dimer complex [Pd 2 Cl 4 (dppbd)] ( 9 ) were characterized in the solid state by a single‐crystal X‐ray structure analysis. Interesting photophysial properties emerged from the UV/Vis spectra acquired for 7 and the dimer Os complexes meso ‐Δ,Λ/Λ,Δ‐[Os 2 (bpy) 4 (dppbd)](PF 6 ) 4 ( 10 ) and rac ‐Δ,Δ/Λ,Λ‐[Os 2 (bpy) 4 (dppbd)](PF 6 ) 4 ( 11 ).