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Stolmàr M, Floriani C, Chiesi-Villa A, et al. p-tert-Butylcalix[4]arene Tetrakis(diphenylphosphinite) and Tetrakis(dimethylphosphinite) Acting as Phosphorus Binding Surfaces for Monometallic and Homo- and Heterodimetallic Fragments. Inorg Chem. 1997;36(8):1694-1701doi: 10.1021/ic9615382.
Stolmàr, M., Floriani, C., Chiesi-Villa, A., & Rizzoli, C. (1997). p-tert-Butylcalix[4]arene Tetrakis(diphenylphosphinite) and Tetrakis(dimethylphosphinite) Acting as Phosphorus Binding Surfaces for Monometallic and Homo- and Heterodimetallic Fragments. Inorganic chemistry, 36(8), 1694-1701. https://doi.org/10.1021/ic9615382
Stolmàr, Matthias, et al. "p-tert-Butylcalix[4]arene Tetrakis(diphenylphosphinite) and Tetrakis(dimethylphosphinite) Acting as Phosphorus Binding Surfaces for Monometallic and Homo- and Heterodimetallic Fragments." Inorganic chemistry vol. 36,8 (1997): 1694-1701. doi: https://doi.org/10.1021/ic9615382
Stolmàr M, Floriani C, Chiesi-Villa A, Rizzoli C. p-tert-Butylcalix[4]arene Tetrakis(diphenylphosphinite) and Tetrakis(dimethylphosphinite) Acting as Phosphorus Binding Surfaces for Monometallic and Homo- and Heterodimetallic Fragments. Inorg Chem. 1997 Apr 09;36(8):1694-1701. doi: 10.1021/ic9615382. PMID: 11669762.
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Inorg Chem. 1997 Apr 09;36(8):1694-1701. doi: 10.1021/ic9615382.

p-tert-Butylcalix[4]arene Tetrakis(diphenylphosphinite) and Tetrakis(dimethylphosphinite) Acting as Phosphorus Binding Surfaces for Monometallic and Homo- and Heterodimetallic Fragments.

Inorganic chemistry

Matthias Stolmàr, Carlo Floriani, Angiola Chiesi-Villa, Corrado Rizzoli

Affiliations

  1. Institut de Chimie Minérale et Analytique, BCH, Université de Lausanne, CH-1015 Lausanne, Switzerland, and Dipartimento di Chimica, Università di Parma, I-43100 Parma, Italy.

PMID: 11669762 DOI: 10.1021/ic9615382

Abstract

p-tert-Butylcalix[4]arene tetrakis(diphenylphosphinite), calix[4]-(PPh(2))(4) (1), and tetrakis(dimethylphosphinite), calix[4]-(PMe(2))(4) (2), provide a phosphorus surface consisting of four coplanar trivalent phosphorus atoms for binding two metal ions into a close geometrical proximity. Homodimetallic complexes have been obtained in the reaction of 1 with [(COD)MCl(2)] [COD = cycloocta-1,5-diene], namely, [{calix[4]-(PPh(2))(4)}(MCl(2))(2)] [M = Pd (3), Pt (4)]. Characterizations by (1)H and (31)P NMR were particularly informative and showed how the bridging methylene of the calix[4]arene skeleton may function as a spectroscopic probe. A dimeric complex was obtained by reacting 1 with [Rh(CO)(2)Cl](2) to give [{calix[4]-(PPh(2))(4)}{Rh(CO)Cl}(2)] (5). Reaction of 1 with excess NiCl(2) gave exclusively the monometallic complex, [{calix[4]-(PPh(2))(4)}NiCl(2)] (6), regardless of the stoichiometry used. The analogous Pd monometallic complex (7) undergoes a ligand disproportionation reaction, while the corresponding Pt analogue does not exist under the same conditions. Complex 6 represents a good entry to dinuclear heterodimetallic complexes. In fact, its reaction with [(NBD)Mo(CO)(4)] [NBD = norbornadiene] led to [{calix[4]-(PPh(2))(4)}NiCl(2){Mo(CO)(4)}] (8). The use of the more basic and less sterically demanding ligand 2 led to the synthesis of homonuclear bimetallic complexes [{calix[4]-(PMe(2))(4)}(MCl(2))(2)] [M = Ni (9), Pd (10), Pt (11)].

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