Aluminum alkyl complexes containing guanidinate ligands

Sarah L. Aeilts; Martyn P. Coles; Dale C. Swenson; Richard F. Jordan; Victor G Young

doi:10.1021/om980223m

Aluminum alkyl complexes containing guanidinate ligands

Sarah L. Aeilts
, Martyn P. Coles
, Dale C. Swenson
, Richard F. Jordan
, Victor G Young

Chemistry (Twin Cities)

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

121 Scopus citations

Abstract

The synthesis and structures of new aluminum complexes incorporating guanidinate ligands (R₂NC(NR′)₂^-) are described. The reaction of ¹PrN=C=NⁱPr with LiNR₂ reagents yields Li[R₂NC(NⁱPr)₂] guanidinate salts, which are reacted in situ with AlCl₃ or AlMe₂Cl to afford {R₂NC(NⁱPr)₂}AlCl₂ (1a, R = Me; 1b, R = Et; 1c, R = ⁱPr; 1d, R = SiMe₃) or {R₂NC(NⁱPr)₂}AlMe₂ (2a, R = Me; 2b, R = Et; 2c, R = ⁱPr), respectively. The reaction of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-α]pyrimidine (hppH) with AlMe₃ generates {(μ-hpp)-AlMe₂}₂ (3). Complexes 1a, 1d, and 3 have been characterized by X-ray crystallography. 1a and 1d adopt monomeric structures with symmetric chelated bidentate guanidinate ligands. Delocalization of the -NR₂ lone pair into the chelate ring is important for 1a but not for 1d, due to N-Si π-bonding and steric crowding. The bicyclic structure of the hpp^- ligand enforces a dimeric μ-hpp^- structure for 3.

Original language	English (US)
Pages (from-to)	3265-3270
Number of pages	6
Journal	Organometallics
Volume	17
Issue number	15
DOIs	https://doi.org/10.1021/om980223m
State	Published - Jul 20 1998

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@article{7d10826fda7d4d04a348dd1866ebc6a7,

title = "Aluminum alkyl complexes containing guanidinate ligands",

abstract = "The synthesis and structures of new aluminum complexes incorporating guanidinate ligands (R2NC(NR′)2-) are described. The reaction of 1PrN=C=NiPr with LiNR2 reagents yields Li[R2NC(NiPr)2] guanidinate salts, which are reacted in situ with AlCl3 or AlMe2Cl to afford \{R2NC(NiPr)2\}AlCl2 (1a, R = Me; 1b, R = Et; 1c, R = iPr; 1d, R = SiMe3) or \{R2NC(NiPr)2\}AlMe2 (2a, R = Me; 2b, R = Et; 2c, R = iPr), respectively. The reaction of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-α]pyrimidine (hppH) with AlMe3 generates \{(μ-hpp)-AlMe2\}2 (3). Complexes 1a, 1d, and 3 have been characterized by X-ray crystallography. 1a and 1d adopt monomeric structures with symmetric chelated bidentate guanidinate ligands. Delocalization of the -NR2 lone pair into the chelate ring is important for 1a but not for 1d, due to N-Si π-bonding and steric crowding. The bicyclic structure of the hpp- ligand enforces a dimeric μ-hpp- structure for 3.",

author = "Aeilts, \{Sarah L.\} and Coles, \{Martyn P.\} and Swenson, \{Dale C.\} and Jordan, \{Richard F.\} and Young, \{Victor G\}",

year = "1998",

month = jul,

day = "20",

doi = "10.1021/om980223m",

language = "English (US)",

volume = "17",

pages = "3265--3270",

journal = "Organometallics",

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publisher = "American Chemical Society",

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T1 - Aluminum alkyl complexes containing guanidinate ligands

AU - Aeilts, Sarah L.

AU - Coles, Martyn P.

AU - Swenson, Dale C.

AU - Jordan, Richard F.

AU - Young, Victor G

PY - 1998/7/20

Y1 - 1998/7/20

N2 - The synthesis and structures of new aluminum complexes incorporating guanidinate ligands (R2NC(NR′)2-) are described. The reaction of 1PrN=C=NiPr with LiNR2 reagents yields Li[R2NC(NiPr)2] guanidinate salts, which are reacted in situ with AlCl3 or AlMe2Cl to afford {R2NC(NiPr)2}AlCl2 (1a, R = Me; 1b, R = Et; 1c, R = iPr; 1d, R = SiMe3) or {R2NC(NiPr)2}AlMe2 (2a, R = Me; 2b, R = Et; 2c, R = iPr), respectively. The reaction of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-α]pyrimidine (hppH) with AlMe3 generates {(μ-hpp)-AlMe2}2 (3). Complexes 1a, 1d, and 3 have been characterized by X-ray crystallography. 1a and 1d adopt monomeric structures with symmetric chelated bidentate guanidinate ligands. Delocalization of the -NR2 lone pair into the chelate ring is important for 1a but not for 1d, due to N-Si π-bonding and steric crowding. The bicyclic structure of the hpp- ligand enforces a dimeric μ-hpp- structure for 3.

AB - The synthesis and structures of new aluminum complexes incorporating guanidinate ligands (R2NC(NR′)2-) are described. The reaction of 1PrN=C=NiPr with LiNR2 reagents yields Li[R2NC(NiPr)2] guanidinate salts, which are reacted in situ with AlCl3 or AlMe2Cl to afford {R2NC(NiPr)2}AlCl2 (1a, R = Me; 1b, R = Et; 1c, R = iPr; 1d, R = SiMe3) or {R2NC(NiPr)2}AlMe2 (2a, R = Me; 2b, R = Et; 2c, R = iPr), respectively. The reaction of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-α]pyrimidine (hppH) with AlMe3 generates {(μ-hpp)-AlMe2}2 (3). Complexes 1a, 1d, and 3 have been characterized by X-ray crystallography. 1a and 1d adopt monomeric structures with symmetric chelated bidentate guanidinate ligands. Delocalization of the -NR2 lone pair into the chelate ring is important for 1a but not for 1d, due to N-Si π-bonding and steric crowding. The bicyclic structure of the hpp- ligand enforces a dimeric μ-hpp- structure for 3.

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U2 - 10.1021/om980223m

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JO - Organometallics

JF - Organometallics

IS - 15

ER -

Aluminum alkyl complexes containing guanidinate ligands

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