Transient Triplet Metallopnictinidenes

by Marc Christian Neben
Doctoral thesis
Date of Examination:2025-04-23
Date of issue:2025-04-30
Advisor:Prof. Dr. Sven Schneider
Referee:Prof. Dr. Sven Schneider
Referee:Prof. Dr. Inke Siewert
Persistent Address: http://dx.doi.org/10.53846/goediss-11241

 

 

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Abstract

English

Nitrenes (N–R) are subvalent key intermediates in organic synthesis and have been extensively studied. The heavier pnictinidene analogues have also attracted great interest, but comprehensive investigations that systematically examine electronic structure trends across extended pnictinidene series are still lacking. The electronic structure of the isolobal Pd and Pt metallonitrenes ([(PNP)M-N]) has been thoroughly examined and revealed a notable impact of transition metal induced spin-orbit coupling. In this work, suitable heavier pnictogen precursor complexes of Pd and Pt were synthesized for the in situ characterization of the corresponding transient metallopnictinidenes ([(PNP)M-Pn], Pn = P, As, Sb). Structural, spectroscopic and computational analysis revealed spin-triplet ground states and distinct electronic structure trends across the series. Beyond the phosphinidene ([(PNP)M-P]), the triplet magnetic microstate splitting becomes increasingly dominated by heavy pnictogen atom induced spin-orbit coupling. This is consistent with energetically lower-lying and more pnictogen localized SOMOs, indicating a more pronounced electrophilic character compared to the nitrenes. Besides the characterization of heavier dipnictenes ([(Pn₂){M(PNP)}₂]) formed via photochemically induced coupling, the impact of electronic structure on the reactivity of the heavier metallopnictinidenes was further examined toward electron-deficient substrates.
Keywords: Coordination Chemistry; Palladium; Platinum; Pnictinidenes; Heavy Pnictogens; Pincer Complexes; Quantum Mechanics
 
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