Cationic, Methylene-Bridged, Intramolecular Donor-Acceptor Systems Based on Zirconium and Hafnium and Phosphino-methanides

Pieper M, Auer P, Schwarzbich S, Kühn F, Neumann B, Stammler H-G, Mitzel NW (2017)
ZEITSCHRIFT FUER ANORGANISCHE UND ALLGEMEINE CHEMIE 643(14): 909-915.

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Abstract
A new access to cationic zirconium and hafnium compounds [L2MCH2PR2][MeB(C6F5)(3)] (L = Cp, Ind; R = iso-Pr, tert-Bu; M = Zr, Hf) exhibiting an intramolecular donor-acceptor system was established by treating the precursors L2M(Me)CH2PR2 with B(C6F5)(3) (BCF). Precursors 1-6 [L2M(Me)CH2PR2 with L = Cp, Ind; R = iso-Pr, tert-Bu; M = Zr, Hf] were fully characterized. The crystal structures of these compounds revealed large M-CH2-P bond angles with values of about 134 degrees indicating the absence of interactions between the Lewis-acid and Lewis-base. The cationic compounds [L2MCH2PR2][MeB(C6F5)(3)] (7-12) were obtained by treatment of 1-6 with BCF. They were characterized by NMR spectroscopy, mass spectrometry, and elemental analyses; in H/D-scrambling experiments with H-2/D-2 mixtures 7-12 disclosed their reactivity towards cleavage of hydrogen.
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Pieper M, Auer P, Schwarzbich S, et al. Cationic, Methylene-Bridged, Intramolecular Donor-Acceptor Systems Based on Zirconium and Hafnium and Phosphino-methanides. ZEITSCHRIFT FUER ANORGANISCHE UND ALLGEMEINE CHEMIE. 2017;643(14):909-915.
Pieper, M., Auer, P., Schwarzbich, S., Kühn, F., Neumann, B., Stammler, H. - G., & Mitzel, N. W. (2017). Cationic, Methylene-Bridged, Intramolecular Donor-Acceptor Systems Based on Zirconium and Hafnium and Phosphino-methanides. ZEITSCHRIFT FUER ANORGANISCHE UND ALLGEMEINE CHEMIE, 643(14), 909-915. doi:10.1002/zaac.201700123
Pieper, M., Auer, P., Schwarzbich, S., Kühn, F., Neumann, B., Stammler, H. - G., and Mitzel, N. W. (2017). Cationic, Methylene-Bridged, Intramolecular Donor-Acceptor Systems Based on Zirconium and Hafnium and Phosphino-methanides. ZEITSCHRIFT FUER ANORGANISCHE UND ALLGEMEINE CHEMIE 643, 909-915.
Pieper, M., et al., 2017. Cationic, Methylene-Bridged, Intramolecular Donor-Acceptor Systems Based on Zirconium and Hafnium and Phosphino-methanides. ZEITSCHRIFT FUER ANORGANISCHE UND ALLGEMEINE CHEMIE, 643(14), p 909-915.
M. Pieper, et al., “Cationic, Methylene-Bridged, Intramolecular Donor-Acceptor Systems Based on Zirconium and Hafnium and Phosphino-methanides”, ZEITSCHRIFT FUER ANORGANISCHE UND ALLGEMEINE CHEMIE, vol. 643, 2017, pp. 909-915.
Pieper, M., Auer, P., Schwarzbich, S., Kühn, F., Neumann, B., Stammler, H.-G., Mitzel, N.W.: Cationic, Methylene-Bridged, Intramolecular Donor-Acceptor Systems Based on Zirconium and Hafnium and Phosphino-methanides. ZEITSCHRIFT FUER ANORGANISCHE UND ALLGEMEINE CHEMIE. 643, 909-915 (2017).
Pieper, Martin, Auer, Pauline, Schwarzbich, Sabrina, Kühn, Franziska, Neumann, Beate, Stammler, Hans-Georg, and Mitzel, Norbert W. “Cationic, Methylene-Bridged, Intramolecular Donor-Acceptor Systems Based on Zirconium and Hafnium and Phosphino-methanides”. ZEITSCHRIFT FUER ANORGANISCHE UND ALLGEMEINE CHEMIE 643.14 (2017): 909-915.
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