Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

Abstract

Introduction 4164 2. P 4 Activation Leading to P 1 , P 2 , and P 3 Products 4165 2.1. Terminal and Bridging P 1 Ligands from P 4 4165 2.2. Bridging P 2 Ligands from P 4 4166 2.3. Cyclo-P 3 Units Derived from P 4 4168 3. P 4 Activation Leading to P 4 Products 4169 3.1. Coordination of P 4 Tetrahedra 4169 3.2. Rearranged P 4 Products 4169 4. P 4 Activation Leading to P g5 Products 4171 5. Functionalization and Transfer Methodologies 4173 5.1. Functionalization and Subsequent Reactivity of Terminal Monophosphide and Bridging Diphosphorus Complexes Derived from P 4 4173 5.2. Reactivity and Transfer Chemistry of the Cyclo-P 3 Functional Group 4174 5.3. Functionalization and Transfer Chemistry of Polyphosphorus Ligands (P g4 ) Derived from P 4 4175 6. Concluding Remarks 4175 6.1. Conclusions 4175 6.2. Future Prospects 4176 7. Acknowledgments 4176 8. References 4176

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

“…Transferring the activated polyphosphide is essential to generate organophosphorus compounds (Cossairt et al, 2010b). The reaction of Sc 3 P 7 or Y 3 P 7 (Scheme 6) with 3 equiv Me3SiI led to the formation of the corresponding rare earth iodide and P7(SiMe3)3 (Huang and Diaconescu, 2012), as confirmed by 31 P NMR spectroscopy (Fritz and Härer, 1983).…”

“…White phosphorous (P4) activation has been long targeted by synthetic chemists (Caporali et al, 2010;Cossairt et al, 2010b;Scheer et al, 2010). Unlike main group elements and late transition metals (Caporali et al, 2010;Scheer et al, 2010), the number of Pn-containing early transition metal complexes formed from direct P4 activation is much smaller (Chirik et al, 2002;Cossairt et al, 2010b;Hey et al, 1987;Scherer et al, 1988;Seidel et al, 2009).…”

“…Unlike main group elements and late transition metals (Caporali et al, 2010;Scheer et al, 2010), the number of Pn-containing early transition metal complexes formed from direct P4 activation is much smaller (Chirik et al, 2002;Cossairt et al, 2010b;Hey et al, 1987;Scherer et al, 1988;Seidel et al, 2009). Among early transition metals, rare earths are more Lewis acidic, leading to a more pronounced mismatch in binding between their ions and phosphorous anions (Cui et al, 2008;Lv et al, 2011;Masuda et al, 2008).…”

P4 Activation by Lanthanum and Lutetium Naphthalene Complexes Supported by a Ferrocene Diamide Ligand

“…Though easily activated, the activation of P4 is not easily controlled. [5][6][7] P4 activation by main group and transition metals has been of long-standing interest. [5][6][7] Alkali metals and late transition metals compose the majority of examples of direct P4 activation.…”

“…[5][6][7] P4 activation by main group and transition metals has been of long-standing interest. [5][6][7] Alkali metals and late transition metals compose the majority of examples of direct P4 activation. [5,6] On the contrary, early transition metal mediated P4 activation is much less investigated and rare-earth examples are rare.…”