Salt metathesis routes to homoleptic near-linear Mg(II) and Ca(II) bulky bis(silyl)amide complexes

Ji-Dong Leng; Conrad Goodwin; Inigo Vitorica-Yrezabal; David Mills

doi:10.1039/c8dt00802g

Salt metathesis routes to homoleptic near-linear Mg(II) and Ca(II) bulky bis(silyl)amide complexes

Ji-Dong Leng, Conrad Goodwin, Inigo Vitorica-Yrezabal, David Mills

Inorganic Chemistry Group

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Abstract

Herein we investigate salt metathesis reactions of bulky bis(silyl)amide potassium salts [K{N(SiMe ₂ ^tBu) ₂}] _n, [K{N(SiMe ₂ ^tBu)(Si ⁱPr ₃)}] _n, [K{N(Si ⁱPr ₃) ₂}] _n and [K{N(SiPh ₃) ₂}] _n (1) with AeI ₂ (Ae = Mg, Ca, Sr) in an effort to synthesise rare homoleptic two-coordinate complexes. Recrystallization of 1 from THF provided structural authentication of the solvated adduct [K{N(SiPh ₃) ₂}(THF) ₃] (1-THF). For Ae = Mg we were able to identify products for three of the four bis(silyl)amides investigated: [Mg{N(SiMe ₂ ^tBu) ₂} ₂(THF)] (2), [Mg{N(SiMe ₂ ^tBu)(Si ⁱPr ₃)} ₂] (3) and [Mg{N(SiPh ₃) ₂} ₂] (4). Complexes 2-4 were isolated in good yields, and on one occasion during recrystallization of 2 a crystal of the heteroleptic complex [Mg{N(SiMe ₂ ^tBu) ₂}(I)(THF) ₂] (5) was identified by XRD. We found that these methodologies were not widely applicable for larger Ae = Ca and Sr, as large quantities of the parent bis(silyl)amines formed in reaction mixtures; however, we were able to isolate the first near-linear Ca(ii) amide [Ca{N(Si ⁱPr ₃) ₂} ₂] (6) from these studies. No Ae-containing products could be isolated from KC ₈/crown ether reductions of 3, 4 and 6. Complexes 1-4 and 6 were characterised by single crystal XRD, multinuclear NMR and FTIR spectroscopy and elemental analysis, whereas complex 5 was identified by single crystal XRD only.

Original language	English
Pages (from-to)	12526-12533
Number of pages	8
Journal	Dalton Transactions
Volume	47
Issue number	36
Early online date	10 Apr 2018
DOIs	https://doi.org/10.1039/c8dt00802g
Publication status	Published - 28 Sept 2018

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@article{a0dfc19c27fe4d17931fe7cd6cc61187,

title = "Salt metathesis routes to homoleptic near-linear Mg(II) and Ca(II) bulky bis(silyl)amide complexes",

abstract = "Herein we investigate salt metathesis reactions of bulky bis(silyl)amide potassium salts [K{N(SiMe 2 tBu) 2}] n, [K{N(SiMe 2 tBu)(Si iPr 3)}] n, [K{N(Si iPr 3) 2}] n and [K{N(SiPh 3) 2}] n (1) with AeI 2 (Ae = Mg, Ca, Sr) in an effort to synthesise rare homoleptic two-coordinate complexes. Recrystallization of 1 from THF provided structural authentication of the solvated adduct [K{N(SiPh 3) 2}(THF) 3] (1-THF). For Ae = Mg we were able to identify products for three of the four bis(silyl)amides investigated: [Mg{N(SiMe 2 tBu) 2} 2(THF)] (2), [Mg{N(SiMe 2 tBu)(Si iPr 3)} 2] (3) and [Mg{N(SiPh 3) 2} 2] (4). Complexes 2-4 were isolated in good yields, and on one occasion during recrystallization of 2 a crystal of the heteroleptic complex [Mg{N(SiMe 2 tBu) 2}(I)(THF) 2] (5) was identified by XRD. We found that these methodologies were not widely applicable for larger Ae = Ca and Sr, as large quantities of the parent bis(silyl)amines formed in reaction mixtures; however, we were able to isolate the first near-linear Ca(ii) amide [Ca{N(Si iPr 3) 2} 2] (6) from these studies. No Ae-containing products could be isolated from KC 8/crown ether reductions of 3, 4 and 6. Complexes 1-4 and 6 were characterised by single crystal XRD, multinuclear NMR and FTIR spectroscopy and elemental analysis, whereas complex 5 was identified by single crystal XRD only. ",

author = "Ji-Dong Leng and Conrad Goodwin and Inigo Vitorica-Yrezabal and David Mills",

note = "Funding Information: This work was supported by the Engineering and Physical Sciences Research Council (Doctoral Prize Fellowship to C. A. P. G.), the International Postdoctoral Exchange Fellowship Program by the Office of China Postdoctoral Council (20140019) and the University of Manchester. J.-D. L. thanks Guangzhou University for a Start-up Fund (2700050362). NMR spectroscopy was supported by EP/ K039547/1 (Core Capability for Chemistry Research: University of Manchester); we gratefully thank Dr Ralph Adams for running 1H DOSY experiments, and for helpful discussions in interpreting the results. We also thank the reviewers for constructive suggestions. Research data files supporting this publication are available from Mendeley Data at DOI: 10.17632/ cdjp7ptvn2.1. Publisher Copyright: {\textcopyright} 2018 The Royal Society of Chemistry.",

year = "2018",

month = sep,

day = "28",

doi = "10.1039/c8dt00802g",

language = "English",

volume = "47",

pages = "12526--12533",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "36",

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TY - JOUR

T1 - Salt metathesis routes to homoleptic near-linear Mg(II) and Ca(II) bulky bis(silyl)amide complexes

AU - Leng, Ji-Dong

AU - Goodwin, Conrad

AU - Vitorica-Yrezabal, Inigo

AU - Mills, David

N1 - Funding Information: This work was supported by the Engineering and Physical Sciences Research Council (Doctoral Prize Fellowship to C. A. P. G.), the International Postdoctoral Exchange Fellowship Program by the Office of China Postdoctoral Council (20140019) and the University of Manchester. J.-D. L. thanks Guangzhou University for a Start-up Fund (2700050362). NMR spectroscopy was supported by EP/ K039547/1 (Core Capability for Chemistry Research: University of Manchester); we gratefully thank Dr Ralph Adams for running 1H DOSY experiments, and for helpful discussions in interpreting the results. We also thank the reviewers for constructive suggestions. Research data files supporting this publication are available from Mendeley Data at DOI: 10.17632/ cdjp7ptvn2.1. Publisher Copyright: © 2018 The Royal Society of Chemistry.

PY - 2018/9/28

Y1 - 2018/9/28

N2 - Herein we investigate salt metathesis reactions of bulky bis(silyl)amide potassium salts [K{N(SiMe 2 tBu) 2}] n, [K{N(SiMe 2 tBu)(Si iPr 3)}] n, [K{N(Si iPr 3) 2}] n and [K{N(SiPh 3) 2}] n (1) with AeI 2 (Ae = Mg, Ca, Sr) in an effort to synthesise rare homoleptic two-coordinate complexes. Recrystallization of 1 from THF provided structural authentication of the solvated adduct [K{N(SiPh 3) 2}(THF) 3] (1-THF). For Ae = Mg we were able to identify products for three of the four bis(silyl)amides investigated: [Mg{N(SiMe 2 tBu) 2} 2(THF)] (2), [Mg{N(SiMe 2 tBu)(Si iPr 3)} 2] (3) and [Mg{N(SiPh 3) 2} 2] (4). Complexes 2-4 were isolated in good yields, and on one occasion during recrystallization of 2 a crystal of the heteroleptic complex [Mg{N(SiMe 2 tBu) 2}(I)(THF) 2] (5) was identified by XRD. We found that these methodologies were not widely applicable for larger Ae = Ca and Sr, as large quantities of the parent bis(silyl)amines formed in reaction mixtures; however, we were able to isolate the first near-linear Ca(ii) amide [Ca{N(Si iPr 3) 2} 2] (6) from these studies. No Ae-containing products could be isolated from KC 8/crown ether reductions of 3, 4 and 6. Complexes 1-4 and 6 were characterised by single crystal XRD, multinuclear NMR and FTIR spectroscopy and elemental analysis, whereas complex 5 was identified by single crystal XRD only.

AB - Herein we investigate salt metathesis reactions of bulky bis(silyl)amide potassium salts [K{N(SiMe 2 tBu) 2}] n, [K{N(SiMe 2 tBu)(Si iPr 3)}] n, [K{N(Si iPr 3) 2}] n and [K{N(SiPh 3) 2}] n (1) with AeI 2 (Ae = Mg, Ca, Sr) in an effort to synthesise rare homoleptic two-coordinate complexes. Recrystallization of 1 from THF provided structural authentication of the solvated adduct [K{N(SiPh 3) 2}(THF) 3] (1-THF). For Ae = Mg we were able to identify products for three of the four bis(silyl)amides investigated: [Mg{N(SiMe 2 tBu) 2} 2(THF)] (2), [Mg{N(SiMe 2 tBu)(Si iPr 3)} 2] (3) and [Mg{N(SiPh 3) 2} 2] (4). Complexes 2-4 were isolated in good yields, and on one occasion during recrystallization of 2 a crystal of the heteroleptic complex [Mg{N(SiMe 2 tBu) 2}(I)(THF) 2] (5) was identified by XRD. We found that these methodologies were not widely applicable for larger Ae = Ca and Sr, as large quantities of the parent bis(silyl)amines formed in reaction mixtures; however, we were able to isolate the first near-linear Ca(ii) amide [Ca{N(Si iPr 3) 2} 2] (6) from these studies. No Ae-containing products could be isolated from KC 8/crown ether reductions of 3, 4 and 6. Complexes 1-4 and 6 were characterised by single crystal XRD, multinuclear NMR and FTIR spectroscopy and elemental analysis, whereas complex 5 was identified by single crystal XRD only.

U2 - 10.1039/c8dt00802g

DO - 10.1039/c8dt00802g

M3 - Article

SN - 1477-9226

VL - 47

SP - 12526

EP - 12533

JO - Dalton Transactions

JF - Dalton Transactions

IS - 36

ER -

Salt metathesis routes to homoleptic near-linear Mg(II) and Ca(II) bulky bis(silyl)amide complexes

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