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Dimer [P2Nb(ODipp)3]2 (Dipp = 2,6-iPr2C6H3) has been obtained via a novel “2(3−1)” synthetic strategy. The mononuclear diphosphorus complex P2Nb(ODipp)3 targeted for generation by formal P− abstraction from previously reported [Na(THF)3][P3Nb(ODipp)3] ostensibly undergoes irreversible dimerization to form the [P2Nb(ODipp)3]2 complex, and is alternatively trapped reversibly by 1,3-cyclohexadiene with in situ formation of C6H8P2Nb(ODipp)3. The molecular structure of [P2Nb(ODipp)3]2 has been determined by X-ray crystallography. Computational studies provide further insights into the bonding and reactivity of P2Nb(ODipp)3, [P2Nb(ODipp)3]2, and C6H8P2Nb(ODipp)3.
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