Homoleptic Trigonal Planar Lanthanide Complexes Stabilized by Superbulky Silylamide Ligands

C A P Goodwin; K C Joslin; S J Lockyer; A Formanuik; G A Morris; F Ortu; I J Vitorica-Yrezabal; D P Mills

doi:10.1021/om501123e

Homoleptic Trigonal Planar Lanthanide Complexes Stabilized by Superbulky Silylamide Ligands

C A P Goodwin, K C Joslin, S J Lockyer, A Formanuik, G A Morris, F Ortu, I J Vitorica-Yrezabal, D P Mills

Inorganic Chemistry Group

Research output: Contribution to journal › Article › peer-review

Abstract

The lithium silylamides [Li(mu(3)-NHSiMe2But)](6) (1) and [Li(mu-NHSiPr3i)(THF)](2), (2) were reacted with ClSiMe3, ClSiMe2But, or ClSiPr3i to prepare a series of secondary silylamines by salt metathesis reactions. These were deprotonated with KH to afford the group 1 transfer agents [K{mu-N(SiMe2But)(SiMe3)/(C7H8)L (3), [{K[mu-N(SiPr3i)(SiMe3)]}(2)](infinity), (4), [{K[mu-N(SiMe2But)(2)]}(2)(C7H8)](infinity) (5), [K{N(SiPr3i)(SiMe2But}](infinity) (6), [KN(SiPri)(2)}](infinity) (7), and [K{N(SiPr3i)(2)}(THF)(3)] (8). The synthetic utility of these group 1 transfer agents has been denionstrated by their reactions with [Ln(I)(3)(THF)(4)] (Ln = La, Ce) In various stoichiometries to yield heteroleptic [La{N(SiMe2But)(SiMe3)}(2)(mu-I)](2) (9), and homoleptic [Ln{N(SiMe2But)(SiMe3)}(3)]. (Ln = La 10, Ce 11) and [La{N(SiMe2But)(2)}(3)] (12). The very-bulky silylamide ligands described herein can impart unusual geometries to their lanthanide complexes. Complexes 10-12 remarkably exhibit approximate planarity in the solid state rather than the more common trigonal pyramidal shapes, observed in previously reported neutral homoleptic lanthanide silylamide complexes. Complexes 1-12 have been variously characterized by X-ray crystallography, NMR spectroscopy, FTIR spectroscopy, and CHN microanalysis.

Original language	English
Pages (from-to)	2314-2325
Number of pages	12
Journal	Organometallics
Volume	34
Issue number	11
DOIs	https://doi.org/10.1021/om501123e
Publication status	Published - 2015

Keywords

x-ray-structure
structural-characterization
crystal-structures
paramagnetic-susceptibility
stickstoff-verbindungen
coordination chemistry
electron-diffraction
molecular-structure
reduction system
nmr-spectra

Access to Document

10.1021/om501123e

CCDC 1032839: Experimental Crystal Structure Determination
Goodwin, C. A. P. (Contributor), Joslin, K. C. (Contributor), Lockyer, S. J. (Contributor), Formanuik, A. (Contributor), Morris, G. (Contributor), Ortu, F. (Contributor), Vitorica-Yrezabal, I. J. (Contributor) & Mills, D. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2015
DOI: 10.5517/cc13nrdx, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc13nrdx&sid=DataCite
Dataset
CCDC 1032841: Experimental Crystal Structure Determination
Goodwin, C. A. P. (Contributor), Joslin, K. C. (Contributor), Lockyer, S. J. (Contributor), Formanuik, A. (Contributor), Morris, G. (Contributor), Ortu, F. (Contributor), Vitorica-Yrezabal, I. J. (Contributor) & Mills, D. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2015
DOI: 10.5517/cc13nrgz, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc13nrgz&sid=DataCite
Dataset
CCDC 1032844: Experimental Crystal Structure Determination
Goodwin, C. A. P. (Contributor), Joslin, K. C. (Contributor), Lockyer, S. J. (Contributor), Formanuik, A. (Contributor), Morris, G. (Contributor), Ortu, F. (Contributor), Vitorica-Yrezabal, I. J. (Contributor) & Mills, D. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2015
DOI: 10.5517/cc13nrk2, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc13nrk2&sid=DataCite
Dataset

Cite this

@article{943485a3d7ea43618b57c5551d180691,

title = "Homoleptic Trigonal Planar Lanthanide Complexes Stabilized by Superbulky Silylamide Ligands",

abstract = "The lithium silylamides [Li(mu(3)-NHSiMe2But)](6) (1) and [Li(mu-NHSiPr3i)(THF)](2), (2) were reacted with ClSiMe3, ClSiMe2But, or ClSiPr3i to prepare a series of secondary silylamines by salt metathesis reactions. These were deprotonated with KH to afford the group 1 transfer agents [K{mu-N(SiMe2But)(SiMe3)/(C7H8)L (3), [{K[mu-N(SiPr3i)(SiMe3)]}(2)](infinity), (4), [{K[mu-N(SiMe2But)(2)]}(2)(C7H8)](infinity) (5), [K{N(SiPr3i)(SiMe2But}](infinity) (6), [KN(SiPri)(2)}](infinity) (7), and [K{N(SiPr3i)(2)}(THF)(3)] (8). The synthetic utility of these group 1 transfer agents has been denionstrated by their reactions with [Ln(I)(3)(THF)(4)] (Ln = La, Ce) In various stoichiometries to yield heteroleptic [La{N(SiMe2But)(SiMe3)}(2)(mu-I)](2) (9), and homoleptic [Ln{N(SiMe2But)(SiMe3)}(3)]. (Ln = La 10, Ce 11) and [La{N(SiMe2But)(2)}(3)] (12). The very-bulky silylamide ligands described herein can impart unusual geometries to their lanthanide complexes. Complexes 10-12 remarkably exhibit approximate planarity in the solid state rather than the more common trigonal pyramidal shapes, observed in previously reported neutral homoleptic lanthanide silylamide complexes. Complexes 1-12 have been variously characterized by X-ray crystallography, NMR spectroscopy, FTIR spectroscopy, and CHN microanalysis.",

keywords = "x-ray-structure, structural-characterization, crystal-structures, paramagnetic-susceptibility, stickstoff-verbindungen, coordination chemistry, electron-diffraction, molecular-structure, reduction system, nmr-spectra",

author = "Goodwin, {C A P} and Joslin, {K C} and Lockyer, {S J} and A Formanuik and Morris, {G A} and F Ortu and Vitorica-Yrezabal, {I J} and Mills, {D P}",

note = "Cl3hu Times Cited:0 Cited References Count:89",

year = "2015",

doi = "10.1021/om501123e",

language = "English",

volume = "34",

pages = "2314--2325",

journal = "Organometallics",

issn = "1520-6041",

publisher = "American Chemical Society",

number = "11",

}

TY - JOUR

T1 - Homoleptic Trigonal Planar Lanthanide Complexes Stabilized by Superbulky Silylamide Ligands

AU - Goodwin, C A P

AU - Joslin, K C

AU - Lockyer, S J

AU - Formanuik, A

AU - Morris, G A

AU - Ortu, F

AU - Vitorica-Yrezabal, I J

AU - Mills, D P

N1 - Cl3hu Times Cited:0 Cited References Count:89

PY - 2015

Y1 - 2015

N2 - The lithium silylamides [Li(mu(3)-NHSiMe2But)](6) (1) and [Li(mu-NHSiPr3i)(THF)](2), (2) were reacted with ClSiMe3, ClSiMe2But, or ClSiPr3i to prepare a series of secondary silylamines by salt metathesis reactions. These were deprotonated with KH to afford the group 1 transfer agents [K{mu-N(SiMe2But)(SiMe3)/(C7H8)L (3), [{K[mu-N(SiPr3i)(SiMe3)]}(2)](infinity), (4), [{K[mu-N(SiMe2But)(2)]}(2)(C7H8)](infinity) (5), [K{N(SiPr3i)(SiMe2But}](infinity) (6), [KN(SiPri)(2)}](infinity) (7), and [K{N(SiPr3i)(2)}(THF)(3)] (8). The synthetic utility of these group 1 transfer agents has been denionstrated by their reactions with [Ln(I)(3)(THF)(4)] (Ln = La, Ce) In various stoichiometries to yield heteroleptic [La{N(SiMe2But)(SiMe3)}(2)(mu-I)](2) (9), and homoleptic [Ln{N(SiMe2But)(SiMe3)}(3)]. (Ln = La 10, Ce 11) and [La{N(SiMe2But)(2)}(3)] (12). The very-bulky silylamide ligands described herein can impart unusual geometries to their lanthanide complexes. Complexes 10-12 remarkably exhibit approximate planarity in the solid state rather than the more common trigonal pyramidal shapes, observed in previously reported neutral homoleptic lanthanide silylamide complexes. Complexes 1-12 have been variously characterized by X-ray crystallography, NMR spectroscopy, FTIR spectroscopy, and CHN microanalysis.

AB - The lithium silylamides [Li(mu(3)-NHSiMe2But)](6) (1) and [Li(mu-NHSiPr3i)(THF)](2), (2) were reacted with ClSiMe3, ClSiMe2But, or ClSiPr3i to prepare a series of secondary silylamines by salt metathesis reactions. These were deprotonated with KH to afford the group 1 transfer agents [K{mu-N(SiMe2But)(SiMe3)/(C7H8)L (3), [{K[mu-N(SiPr3i)(SiMe3)]}(2)](infinity), (4), [{K[mu-N(SiMe2But)(2)]}(2)(C7H8)](infinity) (5), [K{N(SiPr3i)(SiMe2But}](infinity) (6), [KN(SiPri)(2)}](infinity) (7), and [K{N(SiPr3i)(2)}(THF)(3)] (8). The synthetic utility of these group 1 transfer agents has been denionstrated by their reactions with [Ln(I)(3)(THF)(4)] (Ln = La, Ce) In various stoichiometries to yield heteroleptic [La{N(SiMe2But)(SiMe3)}(2)(mu-I)](2) (9), and homoleptic [Ln{N(SiMe2But)(SiMe3)}(3)]. (Ln = La 10, Ce 11) and [La{N(SiMe2But)(2)}(3)] (12). The very-bulky silylamide ligands described herein can impart unusual geometries to their lanthanide complexes. Complexes 10-12 remarkably exhibit approximate planarity in the solid state rather than the more common trigonal pyramidal shapes, observed in previously reported neutral homoleptic lanthanide silylamide complexes. Complexes 1-12 have been variously characterized by X-ray crystallography, NMR spectroscopy, FTIR spectroscopy, and CHN microanalysis.

KW - x-ray-structure

KW - structural-characterization

KW - crystal-structures

KW - paramagnetic-susceptibility

KW - stickstoff-verbindungen

KW - coordination chemistry

KW - electron-diffraction

KW - molecular-structure

KW - reduction system

KW - nmr-spectra

U2 - 10.1021/om501123e

DO - 10.1021/om501123e

M3 - Article

SN - 1520-6041

VL - 34

SP - 2314

EP - 2325

JO - Organometallics

JF - Organometallics

IS - 11

ER -

Homoleptic Trigonal Planar Lanthanide Complexes Stabilized by Superbulky Silylamide Ligands

Abstract

Keywords

Access to Document

Fingerprint

Datasets

CCDC 1032839: Experimental Crystal Structure Determination

CCDC 1032841: Experimental Crystal Structure Determination

CCDC 1032844: Experimental Crystal Structure Determination

Cite this