Molybdenum-Mediated Insertion of Ketones into the P-P bond of cyclo-(P5 Ph5 ) and Formation of Trinuclear Molybdenum Complexes

Elena Gorbachuk; Toni Grell; Khasan Khayarov; Daina Buzyurova; Marat Ziganshin; Timur Mukhametzyanov; Semen Lapuk; Evamarie Hey-Hawkins; Oleg Sinyashin; Dmitry Yakhvarov

doi:10.1002/cplu.202300251

Molybdenum-Mediated Insertion of Ketones into the P-P bond of cyclo-(P₅ Ph₅ ) and Formation of Trinuclear Molybdenum Complexes

Chempluschem. 2023 Aug;88(8):e202300251. doi: 10.1002/cplu.202300251.

Authors

Affiliations

¹ Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzov str., 8, 420088, Kazan, Russian Federation.
² Alexander Butlerov Institute of Chemistry, Kazan Federal University, Kremlyovskaya str., 18, 420008, Kazan, Russian Federation.
³ Department of Chemistry, University of Milan, Via Golgi 19, 20133, Milano, Italy.
⁴ Leipzig University, Institute of Inorganic Chemistry, Johannisallee 29, 04103, Leipzig, Germany.

PMID: 37525541
DOI: 10.1002/cplu.202300251

Abstract

The reaction of cyclopentaphosphine cyclo-(P₅ Ph₅ ) (1) with ketones (acetone and cyclooctanone) in the presence of [Mo(CO)₄ (cod)] (cod=cycloocta-1,5-diene) led to air-stable trinuclear complexes in which the bis-phosphanido ligands (PPh-PPh-PPh-PPh-CMe₂ O-PPh)^2- (complex 2) and (PPh-PPh-PPh-PPh-C(CH₂ )₇ O-PPh)^2- (complex 3) bridge a Mo(CO)₃ -Mo(CO)₃ unit. This extends the reaction of 1 with transition metal carbonyl complexes to further substrates and represents the first examples of insertion of carbonyl compounds into the P-P bond of cyclic oligophosphorus compounds. Complexes 2 and 3 have been characterized by ³¹ P NMR spectroscopy and single crystal X-ray diffraction. Furthermore, the thermal properties of the obtained complexes have been studied by differential scanning calorimetry (DSC) and fast scanning calorimetry (FSC).

Keywords: P−P bond; cyclopentaphosphine; insertion; ketones; thermal properties.

Abstract

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