NDLI: Mechanochemical and solution synthesis, X-ray structure and IR and $^{31}P$ solid state NMR spectroscopic studies of copper( I) thiocyanate adducts with bulky monodentate tertiary phosphine ligands

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Hart, Robert D. King, Scott P. Marchetti, Fabio Tabacaru, Aurel White, Allan H. Pettinari, Claudio Skelton, Brian W. Healy, Peter C. Hanna, John V. Bowmaker, Graham A.
Description	Author Affiliation: Bowmaker GA ( School of Chemical Sciences, University of Auckland, Auckland 1142, New Zealand.)
Abstract	A number of adducts of copper( I) thiocyanate with bulky tertiary phosphine ligands , and some nitrogen -base solvates, were synthesized and structurally and spectroscopically characterised. $CuSCN:PCy_{3}$ (1:2), as crystallized from pyridine , is shown by a single crystal X-ray study to be a one-dimensional polymer $...(Cy_{3}P)_{2}CuSCN(Cy_{3}P)_{2}CuSCN...$ (1) with the four-coordinate copper atoms linked end-on by S-SCN-N bridging thiocyanate groups. A second form (2), obtained from acetonitrile , was also identified and shown by IR and $^{31}P$ CPMAS NMR spectroscopy to be mononuclear, with the magnitude of the $dν_{Cu}$ parameter measured from the $^{31}P$ CPMAS and the ν(CN) value from the IR clearly establishing this compound as three-coordinate $[(Cy_{3}P)_{2}CuNCS].$ Two further $CuSCN/PCy_{3}$ compounds $CuSCN:PCy_{3}$ (1:1) (3), and $CuSCN:PCy_{3}:py$ (1:1:1) (4) were also characterized spectroscopically, with the $dν_{Cu}$ parameters indicating three- and four-coordinate copper sites, respectively. Attempts to obtain a 1:2 adduct with tri- t-butylphosphine have yielded, from pyridine , the 1:1 adduct as a dimer $[(Bu^{t}_{3}P)(^{SCN}_{NCS})Cu(PBu^{t}_{3})]$ (5), while similar attempts with tri- o-tolylphosphine (from acetonitrile and pyridine (= L)) resulted in solvated 1:1:1 $CuSCN:P(o-tol)_{3}:L$ forms as dimeric $[\{(o-tol)_{3}P\}LCu(^{SCN}_{NCS})CuL\{P(o-tol)_{3}\}]$ (6 and 8). The solvent -free 1:1 $CuSCN:P(o-tol)_{3}$ adduct (7), obtained by desolvation of 6, was characterized spectroscopically and $dν_{Cu}$ measurements from the $^{31}P$ CPMAS NMR data are consistent with the decrease in coordination number of the copper atom from four (for 6) (P,N(MeCN)Cu,S,N) to three (for 7) (PCuS,N) upon loss of the acetonitrile of solvation. These results are compared with those previously reported for mononuclear and binuclear $PPh_{3}$ adducts which demonstrate a clear tendency for the copper centre to remain four-coordinate. The IR spectroscopic measurements on these compounds show that bands in the far-IR spectra provide a much more definitive criterion for distinguishing between bridging and terminal bonding than does an often-used empirical rule based on ν(CN) in the mid-IR, which leads to the wrong conclusion in some cases.
ISSN	14779226
Issue Number	25
Volume Number	41
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-07-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Ligands Phosphines Chemistry Thiocyanates Crystallography, X-Ray Magnetic Resonance Spectroscopy Mechanical Phenomena Chemical Synthesis Solutions Spectrophotometry, Infrared Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

Sl.	Authority	Responsibilities	Communication Details
1	Ministry of Education (GoI), Department of Higher Education	Sanctioning Authority	https://www.education.gov.in/ict-initiatives
2	Indian Institute of Technology Kharagpur	Host Institute of the Project: The host institute of the project is responsible for providing infrastructure support and hosting the project	https://www.iitkgp.ac.in
3	National Digital Library of India Office, Indian Institute of Technology Kharagpur	The administrative and infrastructural headquarters of the project	Dr. B. Sutradhar bsutra@ndl.gov.in
4	Project PI / Joint PI	Principal Investigator and Joint Principal Investigators of the project	Dr. B. Sutradhar bsutra@ndl.gov.in Prof. Saswat Chakrabarti will be added soon
5	Website/Portal (Helpdesk)	Queries regarding NDLI and its services	support@ndl.gov.in
6	Contents and Copyright Issues	Queries related to content curation and copyright issues	content@ndl.gov.in
7	National Digital Library of India Club (NDLI Club)	Queries related to NDLI Club formation, support, user awareness program, seminar/symposium, collaboration, social media, promotion, and outreach	clubsupport@ndl.gov.in
8	Digital Preservation Centre (DPC)	Assistance with digitizing and archiving copyright-free printed books	dpc@ndl.gov.in
9	IDR Setup or Support	Queries related to establishment and support of Institutional Digital Repository (IDR) and IDR workshops	idr@ndl.gov.in