Contrasting connectivity of amidine and phosphaamidine (1,3-P,N) Cu(I) complexes

Ramjee Kandel; Keith Huynh; Lauren Dalgliesh; Ruiyao Wang; Philip G. Jessop

doi:10.1016/j.ica.2016.02.024

Contrasting connectivity of amidine and phosphaamidine (1,3-P,N) Cu(I) complexes

Ramjee Kandel
, Keith Huynh
, Lauren Dalgliesh
, Ruiyao Wang
, Philip G. Jessop^*

^*Corresponding author for this work

Queen's University Kingston

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

11 Citations (Scopus)

Abstract

Aprotic acetamidine {Me₂N-C(Me)=N(R)(CuBr)}₂ {R = ⁱPr (2a), Cy (2b), Ph (2c)} and neutral 1,3-P,N phosphaamidine copper bromide complexes {(CuBr)(Ph₂PC(Ph)=NPh)}₄ (6a), {(CuBr)₄(Ph₂PC(Ph)=NⁱPr)₂}·{2CH₂Cl₂} (6b), (CuBr)₄(ⁱPr₂PC(Ph)=NPh)₂} (7a) and {(CuBr)₄(ⁱPr₂PC(Ph)=NⁱPr)₂} (7b) are prepared by direct combination of corresponding amidine and phosphaamidine with CuBr(DMS). X-ray crystallographic analysis of the acetamidine complexes reveal monodentate N_imine coordination to copper with significant degree of delocalization about the N-C=N framework and a relatively short Cu-Cu interaction of 2.5758(8) Å in 2c compared to (2.9801)(10) Å 2a. The phosphaamidine ligands are never η¹-N_imine bound; instead they are η¹-P bound in the cubane complex 6a or η²-bound in the step cluster complexes 6b, 7a and 7b.

Original language	English
Pages (from-to)	117-123
Number of pages	7
Journal	Inorganica Chimica Acta
Volume	445
DOIs	https://doi.org/10.1016/j.ica.2016.02.024
Publication status	Published - 24 Apr 2016
Externally published	Yes

Keywords

Amidines
Copper(I) complexes
Hemilabile ligands
Phosphaamidines

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10.1016/j.ica.2016.02.024

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@article{c09ab38ff86b4c639173e093157ed588,

title = "Contrasting connectivity of amidine and phosphaamidine (1,3-P,N) Cu(I) complexes",

abstract = "Aprotic acetamidine \{Me2N-C(Me)=N(R)(CuBr)\}2 \{R = iPr (2a), Cy (2b), Ph (2c)\} and neutral 1,3-P,N phosphaamidine copper bromide complexes \{(CuBr)(Ph2PC(Ph)=NPh)\}4 (6a), \{(CuBr)4(Ph2PC(Ph)=NiPr)2\}·\{2CH2Cl2\} (6b), (CuBr)4(iPr2PC(Ph)=NPh)2\} (7a) and \{(CuBr)4(iPr2PC(Ph)=NiPr)2\} (7b) are prepared by direct combination of corresponding amidine and phosphaamidine with CuBr(DMS). X-ray crystallographic analysis of the acetamidine complexes reveal monodentate Nimine coordination to copper with significant degree of delocalization about the N-C=N framework and a relatively short Cu-Cu interaction of 2.5758(8) {\AA} in 2c compared to (2.9801)(10) {\AA} 2a. The phosphaamidine ligands are never η1-Nimine bound; instead they are η1-P bound in the cubane complex 6a or η2-bound in the step cluster complexes 6b, 7a and 7b.",

keywords = "Amidines, Copper(I) complexes, Hemilabile ligands, Phosphaamidines",

author = "Ramjee Kandel and Keith Huynh and Lauren Dalgliesh and Ruiyao Wang and Jessop, \{Philip G.\}",

year = "2016",

month = apr,

day = "24",

doi = "10.1016/j.ica.2016.02.024",

language = "English",

volume = "445",

pages = "117--123",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

}

TY - JOUR

T1 - Contrasting connectivity of amidine and phosphaamidine (1,3-P,N) Cu(I) complexes

AU - Kandel, Ramjee

AU - Huynh, Keith

AU - Dalgliesh, Lauren

AU - Wang, Ruiyao

AU - Jessop, Philip G.

PY - 2016/4/24

Y1 - 2016/4/24

N2 - Aprotic acetamidine {Me2N-C(Me)=N(R)(CuBr)}2 {R = iPr (2a), Cy (2b), Ph (2c)} and neutral 1,3-P,N phosphaamidine copper bromide complexes {(CuBr)(Ph2PC(Ph)=NPh)}4 (6a), {(CuBr)4(Ph2PC(Ph)=NiPr)2}·{2CH2Cl2} (6b), (CuBr)4(iPr2PC(Ph)=NPh)2} (7a) and {(CuBr)4(iPr2PC(Ph)=NiPr)2} (7b) are prepared by direct combination of corresponding amidine and phosphaamidine with CuBr(DMS). X-ray crystallographic analysis of the acetamidine complexes reveal monodentate Nimine coordination to copper with significant degree of delocalization about the N-C=N framework and a relatively short Cu-Cu interaction of 2.5758(8) Å in 2c compared to (2.9801)(10) Å 2a. The phosphaamidine ligands are never η1-Nimine bound; instead they are η1-P bound in the cubane complex 6a or η2-bound in the step cluster complexes 6b, 7a and 7b.

AB - Aprotic acetamidine {Me2N-C(Me)=N(R)(CuBr)}2 {R = iPr (2a), Cy (2b), Ph (2c)} and neutral 1,3-P,N phosphaamidine copper bromide complexes {(CuBr)(Ph2PC(Ph)=NPh)}4 (6a), {(CuBr)4(Ph2PC(Ph)=NiPr)2}·{2CH2Cl2} (6b), (CuBr)4(iPr2PC(Ph)=NPh)2} (7a) and {(CuBr)4(iPr2PC(Ph)=NiPr)2} (7b) are prepared by direct combination of corresponding amidine and phosphaamidine with CuBr(DMS). X-ray crystallographic analysis of the acetamidine complexes reveal monodentate Nimine coordination to copper with significant degree of delocalization about the N-C=N framework and a relatively short Cu-Cu interaction of 2.5758(8) Å in 2c compared to (2.9801)(10) Å 2a. The phosphaamidine ligands are never η1-Nimine bound; instead they are η1-P bound in the cubane complex 6a or η2-bound in the step cluster complexes 6b, 7a and 7b.

KW - Amidines

KW - Copper(I) complexes

KW - Hemilabile ligands

KW - Phosphaamidines

UR - https://www.scopus.com/pages/publications/84966264003

U2 - 10.1016/j.ica.2016.02.024

DO - 10.1016/j.ica.2016.02.024

M3 - Article

AN - SCOPUS:84966264003

SN - 0020-1693

VL - 445

SP - 117

EP - 123

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Contrasting connectivity of amidine and phosphaamidine (1,3-P,N) Cu(I) complexes

Abstract

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