TY - JOUR
T1 - Reactivity of elemental tin and zinc toward organophosphonic acid dialkyl esters
T2 - a new one-pot recipe for the synthesis of coordination assemblies derived from o-alkylorganophosphonate ligands
AU - Shankar, Ravi
AU - Mendiratta, Swati
AU - Singla, Nisha
AU - Kociok-Kohn, Gabriele
AU - Lutter, Michael
AU - Jurkschat, Klaus
PY - 2017/1/17
Y1 - 2017/1/17
N2 - A new recipe for the synthesis of diorganotin bis(O-alkylorganophosphonate)s, R1 2Sn{O- (P)(O)(OR1)R}2 [R = R1 = methyl (1); R1 = ethyl and R = methyl (2), allyl (3), 2-thienyl (4), benzyl (5)], has been developed from the direct reaction of elemental tin (powder) with organophosphonic acid dialkyl esters, RP(O)(OR1)2, in the presence of a catalytic amount of potassium iodide under ambient conditions (130 °C, 18-20 h). The key steps in the proposed catalytic cycle involve the monodealkylation of phosphonate diester and in situ generation of a R1SnI or R1 2SnI2 intermediate via the oxidative addition of alkyl iodide on tin. Evidence in support of the formation of organotin species comes from the isolation of Me2Sn{O(P)(O)(OiPr)Me}2 (6) from the direct reaction of tin metal with MeP(O)(OiPr)2 in the presence of methyl iodide. The method has also been extended to isolate Zn{OP(O)(OMe)Me}2 (7) using metallic zinc as the precursor. All of the compounds have been characterized by IR and NMR studies as well as X-ray crystallography for 2, 4, 6, and 7.
AB - A new recipe for the synthesis of diorganotin bis(O-alkylorganophosphonate)s, R1 2Sn{O- (P)(O)(OR1)R}2 [R = R1 = methyl (1); R1 = ethyl and R = methyl (2), allyl (3), 2-thienyl (4), benzyl (5)], has been developed from the direct reaction of elemental tin (powder) with organophosphonic acid dialkyl esters, RP(O)(OR1)2, in the presence of a catalytic amount of potassium iodide under ambient conditions (130 °C, 18-20 h). The key steps in the proposed catalytic cycle involve the monodealkylation of phosphonate diester and in situ generation of a R1SnI or R1 2SnI2 intermediate via the oxidative addition of alkyl iodide on tin. Evidence in support of the formation of organotin species comes from the isolation of Me2Sn{O(P)(O)(OiPr)Me}2 (6) from the direct reaction of tin metal with MeP(O)(OiPr)2 in the presence of methyl iodide. The method has also been extended to isolate Zn{OP(O)(OMe)Me}2 (7) using metallic zinc as the precursor. All of the compounds have been characterized by IR and NMR studies as well as X-ray crystallography for 2, 4, 6, and 7.
UR - http://www.scopus.com/inward/record.url?scp=85009727889&partnerID=8YFLogxK
UR - http://dx.doi.org/10.1021/acs.inorgchem.6b02789
U2 - 10.1021/acs.inorgchem.6b02789
DO - 10.1021/acs.inorgchem.6b02789
M3 - Article
AN - SCOPUS:85009727889
SN - 0020-1669
VL - 56
SP - 721
EP - 724
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 2
ER -