Trans-spanning ligand

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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.

Contents

Trans vs cis ligand.png

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.

Structure of PtCl2(SPANphos) WABXIH.png
Structure of PtCl2(SPANphos)

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.

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References

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  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.
  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.