Trans-spanning ligand

Trans-spanning ligands are bidentate ligands that can span opposite sites of a complex with square-planar geometry. A wide variety of ligands that chelate in the cis fashion already exist, but very few can link opposite vertices on a coordination polyhedron. Early attempts to generate trans-spanning bidentate ligands relied on long hydrocarbon chains to link the donor functionalities, but such ligands often lead to coordination polymers.

History

A diphosphane linked with pentamethylene was claimed to span across a square planar complex. This early attempt was followed by ligands with more rigid backbones. "TRANSPHOS" was the first trans-spanning diphosphane ligand that usually coordinates to palladium(II) and platinum(II) in a trans manner. TRANSPHOS features benzo[c]phenanthrene substituted by diphenylphosphinomethyl (Ph₂PCH₂) groups at the 1 and 11 positions.^[1]^[2] The polycyclic framework suffers sterically clashing hydrogen centers.

SPANphos, TRANSDIP, and related ligands

Structure of PtCl₂(SPANphos)^[3]

TRANSDIP, based on a α-cyclodextrin, is the first ligand to give exclusively trans-spanned complexes, even with d⁸ metal ion halides.^[4] Xantphos is sometimes classified as a trans-spanning ligand, with less steric bulk compared to TRANSPHOS. SPANphos is comparable to XANTPHOS but more reliably trans-spanning.

References

^ Destefano, N. J.; Johnson, D. K.; Lane, R. M.; Venanzi, L. M. (1976). "Transition-Metal Complexes with Bidentate Ligands Spanning Trans-Positions. I. The Synthesis of 2,11-Bis(Diphenylphosphinomethyl)Benzo[C]-Phenanthrene, A Ligand Promoting the Formation of Square Planar Complexes". Helvetica Chimica Acta. 59 (8): 2674–2682. doi:10.1002/hlca.19760590806.
^ Mochida, J. A.; Mattern, J. C.; Bailar, J. Jr. (1975). "Stereochemistry of Complex Inorganic Compounds. XXXV. A Complex Containing a Ligand That Spans Trans Positions". J. Am. Chem. Soc. 97 (11): 3021–3026. doi:10.1021/ja00844a017.
^ Z. Freixa, M. S. Beentjes, G. D. Batema, C. B. Dieleman, G. P. F. van Strijdonck, J. N. H. Reek, P. C. J. Kamer, J. Fraanje, K. Goubitz and P. W. N. M. van Leeuwen (2003). "SPANphos: A C₂-Symmetric trans-Coordinating Diphosphane Ligand". Angewandte Chemie International Edition. 42 (11): 1322–1325. doi:10.1002/anie.200390330. PMID 12645065.{{cite journal}}: CS1 maint: multiple names: authors list (link)
^ Poorters, L.; Armspach, D.; Matt, D.; Toupet, L.; Choua, S.; Turek, P. (2007). "Synthesis and Properties of Transdip, A Rigid Chelator Built Upon a Cyclodextrin Cavity: is Transdip an Authentic Trans - Spanning Ligand?" (PDF). Chemistry: A European Journal. 13 (34): 9448–9461. doi:10.1002/chem.200700831. PMID 17943701.

[1] Destefano, N. J.; Johnson, D. K.; Lane, R. M.; Venanzi, L. M. (1976). "Transition-Metal Complexes with Bidentate Ligands Spanning Trans-Positions. I. The Synthesis of 2,11-Bis(Diphenylphosphinomethyl)Benzo[C]-Phenanthrene, A Ligand Promoting the Formation of Square Planar Complexes". Helvetica Chimica Acta. 59 (8): 2674–2682. doi:10.1002/hlca.19760590806.

[2] Mochida, J. A.; Mattern, J. C.; Bailar, J. Jr. (1975). "Stereochemistry of Complex Inorganic Compounds. XXXV. A Complex Containing a Ligand That Spans Trans Positions". J. Am. Chem. Soc. 97 (11): 3021–3026. doi:10.1021/ja00844a017.

[Freixa-3] Z. Freixa, M. S. Beentjes, G. D. Batema, C. B. Dieleman, G. P. F. van Strijdonck, J. N. H. Reek, P. C. J. Kamer, J. Fraanje, K. Goubitz and P. W. N. M. van Leeuwen (2003). "SPANphos: A C₂-Symmetric trans-Coordinating Diphosphane Ligand". Angewandte Chemie International Edition. 42 (11): 1322–1325. doi:10.1002/anie.200390330. PMID 12645065.{{cite journal}}: CS1 maint: multiple names: authors list (link)

[4] Poorters, L.; Armspach, D.; Matt, D.; Toupet, L.; Choua, S.; Turek, P. (2007). "Synthesis and Properties of Transdip, A Rigid Chelator Built Upon a Cyclodextrin Cavity: is Transdip an Authentic Trans - Spanning Ligand?" (PDF). Chemistry: A European Journal. 13 (34): 9448–9461. doi:10.1002/chem.200700831. PMID 17943701.

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