Eight-co-ordination in lanthanide pyrazolylborate chemistry: crystal structures of [LaTpMe,Me2(MeCN)(O3SCF3)] ·MeCN, [NdTpMe,Me2(MeCN)2][O3SCF 3] and [LaTpMe,Me2(NO3)]·MeCN [TpMe,Me = tris(3,5-dimethylpyrazolyl) hydroborate]

Clark, Robin J. H.; Liu, Sung Ying; Maunder, Graham H.; Sella, Andrea; Elsegood, Mark R. J.

doi:10.1039/a608620i

Cited by 15 publications

(14 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The trapezoids are almost planar, with normalized φ angles of 0.6°and 2.2°. The average La-N(Tp) distance is 2.68(6) Å (range 2.612-(10)-2.751(10) Å), a value in line with those of 2.645 (7) and 2.647(3) Å in [La(Tp Me2 ) 2 (MeCN)(O 3 SCF 3 )] and [La(Tp Me2 ) 2 (NO 3 )], 29 respectively, but 0.08 Å larger than the corresponding values in the mono-Tp Me2 compounds (2.600-(4) Å in 2 and 2.604 Å in 4). The increased coordination number for 7 is also reflected in the long average La-N distance to the bipyridyl of 2.620(10) Å, 0.1 Å larger than the values of 2.432(2) and 2.32 Å found in Cp* 2 Sm(bipy) 4 and Cp* 2 Yb(bipy), 5 respectively, after correction of the ionic radii.…”

Section: Reduction Of 1 and 2 With Sodium Amalgam: A New Route For Co...supporting

confidence: 75%

“…28 This coordination geometry has been found already in other [Sm(Tp Me2 ) 2 (X-X)] compounds. 25,29 The intersecting trapezoids (defined by the atoms N12, N2, N1, N62 and N22, N32, N42, N52) make a dihedral angle of 82°rather than the ideal 90°. The trapezoids are almost planar, with normalized φ angles of 0.6°and 2.2°.…”

Section: Reduction Of 1 and 2 With Sodium Amalgam: A New Route For Co...mentioning

confidence: 99%

See 1 more Smart Citation

Coordination of 2,2‘-Bipyridyl and 1,10-Phenanthroline to Yttrium and Lanthanum Complexes Based on a Scorpionate Ligand

Roitershtein¹,

Domingos²,

Pereira³

et al. 2003

Inorg. Chem.

View full text Add to dashboard Cite

Reaction of yttrium and lanthanum trichloride with 1 equiv of sodium or potassium hydrotris(3,5-dimethylpyrazolyl)borate and 1 equiv of 2,2'-bipyridine gives good yields of the complexes [MCl(2)(Tp(Me2))(C(10)H(8)N(2))] (M = Y (1), La (2)). The analogous compounds with 1,10-phenanthroline, [MCl(2)(Tp(Me2))(C(12)H(8)N(2))] (M = Y (3), La (4)), have been obtained by a similar procedure. The solid-state structures of 2-4 were determined by single-crystal X-ray diffraction and revealed that the compounds are all seven-coordinate with capped octahedral geometry. In contrast, reaction of yttrium trichloride with 1 equiv of sodium hydrotris(3,5-dimethylpyrazolyl)borate in the presence of 1 equiv of neocuproine affords [YCl(3)(Tp(Me2))][Na(neoc)(3))] (5). Compounds 1 and 2 provide an entry for the synthesis of complexes containing the bipyridyl ligand in a radical anionic form or in a dianionic form. Reaction of 1 and 2 with an excess of sodium amalgam gives [Y(Tp(Me2))(bipy)(THF)(2)] (6) and [La(Tp(Me2))(2)(bipy)] (7), respectively. The structures of both compounds have been determined by X-ray crystallography. Compound 7 can be oxidized with iodine to give [La(Tp(Me2))(2)(bipy)]I (8).

show abstract

Section: Reduction Of 1 and 2 With Sodium Amalgam: A New Route For Co...supporting

confidence: 75%

Section: Reduction Of 1 and 2 With Sodium Amalgam: A New Route For Co...mentioning

confidence: 99%

Coordination of 2,2‘-Bipyridyl and 1,10-Phenanthroline to Yttrium and Lanthanum Complexes Based on a Scorpionate Ligand

Roitershtein¹,

Domingos²,

Pereira³

et al. 2003

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

“…Thus, the structure is rather similar to that observed previously for [La(Tp Me 2) 2 (NO 3 )] in which the nitrate group tightens the base of the dodecahedron and lowers the symmetry toward C 2 . 6 The two pyrazolylborate groups are mutually staggered and bent back with a B-Sm-B angle of 137.2°comparable to that observed in [Nd(Tp Me 2) 2 (MeCN) 2 ](O 3 SCF 3 ) (137°). 6 This bend angle is considerably smaller than in the comparable eightcoordinate complexes [Sm(Tp Me 2) 2 (O 2 )] (144.1°), 5b [Sm(Tp Me 2) 2 -(PhNNPh)] (152.6°), 5a [Sm(Tp Me 2 ,4-Et ) 2 (NO 2 )] (159.0°), 18 [La(Tp Me 2) 2 (NO 3 )] (143.6°), 6 and [La(Tp Me 2) 2 (MeCN)(O 3 -SCF 3 )] (142.7°) 6 and may be a reflection of the greater steric demand of the second-row donor atoms of the dithiocarbamate.…”

Section: [Sm(tp Mementioning

confidence: 81%

“…6 The two pyrazolylborate groups are mutually staggered and bent back with a B-Sm-B angle of 137.2°comparable to that observed in [Nd(Tp Me 2) 2 (MeCN) 2 ](O 3 SCF 3 ) (137°). 6 This bend angle is considerably smaller than in the comparable eightcoordinate complexes [Sm(Tp Me 2) 2 (O 2 )] (144.1°), 5b [Sm(Tp Me 2) 2 -(PhNNPh)] (152.6°), 5a [Sm(Tp Me 2 ,4-Et ) 2 (NO 2 )] (159.0°), 18 [La(Tp Me 2) 2 (NO 3 )] (143.6°), 6 and [La(Tp Me 2) 2 (MeCN)(O 3 -SCF 3 )] (142.7°) 6 and may be a reflection of the greater steric demand of the second-row donor atoms of the dithiocarbamate. This is probably also responsible for the longer average Sm-Npz distance in 1 (2.626(6) Å) (range 2.503(5)-2.728(5) Å) than in [Sm(Tp Me 2) 2 (O 2 )] (2.58 Å), 5b [Sm(Tp Me 2) 2 (PhNNPh)] (2.59 Å), 5a and [Sm(Tp Me 2 ,4-Et ) 2 (NO 2 )] (2.559(4) Å).…”

Section: [Sm(tp Mementioning

confidence: 81%

Solid-State Structure and Solution Behavior of Eight-Coordinate Sm(III) Poly(pyrazolyl)borate Compounds

Lopes¹,

Ac²,

Sy³

et al. 2001

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

[Sm(Tp(Me2)(2)(kappa(2)-S(2)CNR(2))] compounds (R = Et (1), Me (2); Tp(Me2) = HB(3,5-Me2pz)(3)) have been isolated from reaction of (R(2)NC(S)S)(2) with 2 equiv of [Sm(Tp(Me2)(2)]. Reductive cleavage of 2,2'-dipyridyl disulfide or 2,2'-dipyridyl diselenide by [Sm(Tp(Me2)(2)] afforded good yields of [Sm(Tp(Me2)(2)(kappa(2)-Y)] compounds (Y = 2-SC(5)H(4)N (3), 2-SeC(5)H(4)N (4)). 4 is the first selenopyridine complex of an f-block element. Sm(Tp(Me2)(2)(2-OC(5)H(4)N) (5) has been synthesized by salt metathesis of [Sm(Tp(Me2)(2)Cl] with the sodium salt of the 2-hydroxypyridine. The solid-state structures of 1, 3, 4, and 5 were determined by single-crystal X-ray diffraction analysis and revealed that the compounds are all eight-coordinate with dodecahedral geometry. The samarium atoms are bound in tridentate fashion to two pyrazolylborate ligands and in bidentate fashion by the third ligand. The solution behavior of the compounds was studied by (1)H NMR techniques. (1)H-(1)H exchange spectroscopy experiments give evidence for two distinct dynamic regimes occurring in solution.

show abstract

“…The presence of the electron-withdrawing triflato moieties implies also slightly shorter LuÀC(Me) distances of 1-Lu (2.327(4) )a nd 3-Lu (2.323(2) )t han those in the precursor [Tp tBu,Me LuMe 2 ] [24] (2.364(3)/2.375 (2) ). Despite several achievements on the structuralc haracterization of various Tp-supported LnÀOTf complexes, [28] mixed Me/OTf and Me/NTf 2 structural motifs have not yet been identified. So far,t he structurally authenticated complexes comprise "sandwich complexes" exclusively, namely sevenfold-coordinated [(Tp Me,Me ) 2 Nd(OTf)] (NdÀO, 2.421(5) ), sixfold-coordinated [{(Tp Me,Me ) 2 Yb}(OTf)],e ightfold- To target the envisaged LnMeX to Ln = CH 2 transformation (see Scheme 1/path A)c omplexes [Tp tBu,Me LuMeX] (X = OTf, 1-Lu;N Tf 2 , 3-Lu) were treated with one equivalent of H 2 CPPh 3 in [D 6 ]benzene.…”

Section: "Half-sandwich" Triflatecomplexesmentioning

confidence: 99%

Potential Precursors for Terminal Methylidene Rare‐Earth‐Metal Complexes Supported by a Superbulky Tris(pyrazolyl)borato Ligand

Birkelbach

Thim

Stuhl

et al. 2019

Chemistry A European J

View full text Add to dashboard Cite

A series of solvent‐free heteroleptic terminal rare‐earth‐metal alkyl complexes stabilized by a superbulky tris(pyrazolyl)borato ligand with the general formula [TptBu,MeLnMeR] have been synthesized and fully characterized. Treatment of the heterobimetallic mixed methyl/tetramethylaluminate compounds [TptBu,MeLnMe(AlMe4)] (Ln=Y, Lu) with two equivalents of the mild halogenido transfer reagents SiMe3X (X=Cl, I) gave [TptBu,MeLnX2] in high yields. The addition of only one equivalent of SiMe3Cl to [TptBu,MeLuMe(AlMe4)] selectively afforded the desired mixed methyl/chloride complex [TptBu,MeLuMeCl]. Further reactivity studies of [TptBu,MeLuMeCl] with LiR or KR (R=CH2Ph, CH2SiMe3) through salt metathesis led to the monomeric mixed‐alkyl derivatives [TptBu,MeLuMe(CH2SiMe3)] and [TptBu,MeLuMe(CH2Ph)], respectively, in good yields. The SiMe4 elimination protocols were also applicable when using SiMe3X featuring more weakly coordinating moieties (here X=OTf, NTf2). X‐ray structure analyses of this diverse set of new [TptBu,MeLnMeR/X] compounds were performed to reveal any electronic and steric effects of the varying monoanionic ligands R and X, including exact cone‐angle calculations of the tridentate tris(pyrazolyl)borato ligand. Deeper insights into the reactivity of these potential precursors for terminal alkylidene rare‐earth‐metal complexes were gained through NMR spectroscopic studies.

show abstract

Eight-co-ordination in lanthanide pyrazolylborate chemistry: crystal structures of [LaTpMe,Me2(MeCN)(O3SCF3)] ·MeCN, [NdTpMe,Me2(MeCN)2][O3SCF 3] and [LaTpMe,Me2(NO3)]·MeCN [TpMe,Me = tris(3,5-dimethylpyrazolyl) hydroborate]

Cited by 15 publications

References 13 publications

Coordination of 2,2‘-Bipyridyl and 1,10-Phenanthroline to Yttrium and Lanthanum Complexes Based on a Scorpionate Ligand

Coordination of 2,2‘-Bipyridyl and 1,10-Phenanthroline to Yttrium and Lanthanum Complexes Based on a Scorpionate Ligand

Solid-State Structure and Solution Behavior of Eight-Coordinate Sm(III) Poly(pyrazolyl)borate Compounds

Potential Precursors for Terminal Methylidene Rare‐Earth‐Metal Complexes Supported by a Superbulky Tris(pyrazolyl)borato Ligand

Contact Info

Product

Resources

About