When Metathesis Reactions Go Wrong: Novel Structural Consequences

Beaini, Samar; Deacon, Glen B.; Forsyth, Craig M.; Junk, Peter Courtney

doi:10.1002/zaac.200800325

Cited by 3 publications

(1 citation statement)

References 20 publications

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“…Average Ln-N bond length differences in the nine-coordinate Ph 2 pz complexes (0.018, 0.028 and 0.049 Å for RE = Nd, Eu and Er, respectively) are smaller than those of 8a, 8b and 9, whereas in eightcoordinate [Yb(Ph 2 pz) 3 (dme)], [16] two of three Ph 2 pz ligands are substantially asymmetrically chelated. Centroid angles [a] cen{O (1) In comparison with ten-coordinate 8a, 8b and 9 and nine-coordinate [Eu(Ph 2 pz) 3 (dme) 2 ], [19] the eight-coordinate anion in the charge-separated [Li(dme) 3 ][Eu II (η 2 -Ph 2 pz) 3 -(dme)] [30] complex appears to be a structural anomaly, since Eu 2+ possesses a larger ionic radius than Eu 3+ . Possibly, the lower charge on the metal together with the anionic nature of the complex leads to coordination saturation without steric saturation.…”

Section: [Re(ttfpz) 3 (Dme) 2 ]·Nsolv Complexesmentioning

confidence: 99%

Trivalent Rare Earth Complexes of the Unsymmetrical 3‐(2′‐Thienyl)‐5‐(trifluoromethyl)pyrazolate Ligand

2011

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Trivalent rare earth complexes of the unsymmetrical 3-(2Ј-thienyl)-5-(trifluoromethyl)pyrazolate (ttfpz) ligand, namely [RE(ttfpz) 3 (thf) 3 ]·nsolv, where thf = tetrahydrofuran [RE = La, solv = PhMe, n = 0.5 (1); RE = Sm, n = 0 (2); RE = Tb, solv = thf, n = 1 (3)], [RE(ttfpz) 3 (thf) 2 ] [RE = Y (4), Ho (5), Lu (6), Sc (7)] and [RE(ttfpz) 3 (dme) 2 ]·nsolv, where dme = 1,2-dimethoxyethane [RE = La, n = 0 (8a); RE = La, solv = Et 2 O, n = 0.5 (8b); RE = Eu, solv = dme, n = 1 (9)], were prepared, mainly by redox transmetallation/protolysis from the free metal, Hg(C 6 F 5 ) 2 and ttfpzH, and structurally characterised. In the nine-coordinate, pseudo-octahedral complexes 1 and 2, η 2 -

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Section: [Re(ttfpz) 3 (Dme) 2 ]·Nsolv Complexesmentioning

confidence: 99%

Trivalent Rare Earth Complexes of the Unsymmetrical 3‐(2′‐Thienyl)‐5‐(trifluoromethyl)pyrazolate Ligand

2011

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Expanding Yttrium Bis(trimethylsilylamide) Chemistry Through the Reaction Chemistry of (N₂)^2–, (N₂)^3–, and (NO)^2– Complexes

2012

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The reaction chemistry of the side-on bound (N(2))(2-), (N(2))(3-), and (NO)(2-) complexes of the [(R(2)N)(2)Y](+) cation (R = SiMe(3)), namely, [(R(2)N)(2)(THF)Y](2)(μ-η(2):η(2)-N(2)), 1, [(R(2)N)(2)(THF)Y](2)(μ-η(2):η(2)-N(2))K, 2, and [(R(2)N)(2)(THF)Y](2)(μ-η(2):η(2)-NO), 3, with oxidizing agents has been explored to search for other (E(2))(n-), (E = N, O), species that can be stabilized by this cation. This has led to the first examples for the [(R(2)N)(2)Y](+) cation of two fundamental classes of [(monoanion)(2)Ln](+) rare earth systems (Ln = Sc, Y, lanthanides), namely, oxide complexes and the tetraphenylborate salt. In addition, an unusually high yield reaction with dioxygen was found to give a peroxide complex that completes the (N(2))(2-), (NO)(2-), (O(2))(2-) series with 1 and 3. Specifically, the (μ-O)(2-) oxide-bridged bimetallic complex, [(R(2)N)(2)(THF)Y}(2)(μ-O), 4, is obtained as a byproduct from reactions of either the (N(2))(2-) complex, 1, or the (N(2))(3-) complex, 2, with NO, while the oxide formed from 2 with N(2)O is a polymeric species incorporating potassium, {[(R(2)N)(2)Y](2)(μ-O)(2)K(2)(μ-C(7)H(8))}(n), 5. Reaction of 1 with 1 atm of O(2) generates the (O(2))(2-) bridging side-on peroxide [(R(2)N)(2)(THF)Y](2)(μ-η(2):η(2)-O(2)), 6. The O-O bond in 6 is cleaved by KC(8) to provide an alternative synthetic route to 5. Attempts to oxidize the (NO)(2-) complex, 3, with AgBPh(4) led to the isolation of the tetraphenylborate complex, [(R(2)N)(2)Y(THF)(3)][BPh(4)], 7, that was also synthesized from 1 and AgBPh(4). Oxidation of the (N(2))(2-) complex, 1, with the radical trap (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, TEMPO, generates the (TEMPO)(-) anion complex, (R(2)N)(2)(THF)Y(η(2)-ONC(5)H(6)Me(4)), 8.

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Divalent metal complexes (Ca, Sr, Ba, Yb) of the unsymmetrical 3-(2′-thienyl)-5-(trifluoromethyl)pyrazolate ligand

2011

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The divalent complexes [M(ttfpz)(2)(thf)(4)] (ttfpz = 3-(2'-thienyl)-5-(trifluoromethyl)pyrazolate; M = Yb, 1, Ca, 2, Sr, 3, Ba, 4; thf = tetrahydrofuran) and [M(ttfpz)(2)(dme)(n)] (M = Ca, 5, Sr, 6, Yb, 7, n = 2; M = Ba, 8, n = 3; dme = 1,2-dimethoxyethane) have been prepared by redox transmetallation/protolysis reactions employing the free metals, Hg(C(6)F(5))(2) and ttfpzH in donor solvents and their structures determined. The monomeric structures exhibit η(2)-bound pyrazolate ligands with eight-coordinate metal atoms for complexes 1-7 and a ten-coordinate metal for 8. The pyrazolate ligands in the thf-complexes 1-4 as well as dme-derivatives 5 and 6 are in a transoid configuration, whilst in complex 7 the ttfpz ligands exhibit a cisoid relationship. In 8 the ligands have an intermediate role in between cisoid and transoid.

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When Metathesis Reactions Go Wrong: Novel Structural Consequences

Cited by 3 publications

References 20 publications

Trivalent Rare Earth Complexes of the Unsymmetrical 3‐(2′‐Thienyl)‐5‐(trifluoromethyl)pyrazolate Ligand

Trivalent Rare Earth Complexes of the Unsymmetrical 3‐(2′‐Thienyl)‐5‐(trifluoromethyl)pyrazolate Ligand

Expanding Yttrium Bis(trimethylsilylamide) Chemistry Through the Reaction Chemistry of (N₂)^2–, (N₂)^3–, and (NO)^2– Complexes

Divalent metal complexes (Ca, Sr, Ba, Yb) of the unsymmetrical 3-(2′-thienyl)-5-(trifluoromethyl)pyrazolate ligand

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When Metathesis Reactions Go Wrong: Novel Structural Consequences

Cited by 3 publications

References 20 publications

Trivalent Rare Earth Complexes of the Unsymmetrical 3‐(2′‐Thienyl)‐5‐(trifluoromethyl)pyrazolate Ligand

Trivalent Rare Earth Complexes of the Unsymmetrical 3‐(2′‐Thienyl)‐5‐(trifluoromethyl)pyrazolate Ligand

Expanding Yttrium Bis(trimethylsilylamide) Chemistry Through the Reaction Chemistry of (N2)2–, (N2)3–, and (NO)2– Complexes

Divalent metal complexes (Ca, Sr, Ba, Yb) of the unsymmetrical 3-(2′-thienyl)-5-(trifluoromethyl)pyrazolate ligand

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Expanding Yttrium Bis(trimethylsilylamide) Chemistry Through the Reaction Chemistry of (N₂)^2–, (N₂)^3–, and (NO)^2– Complexes