{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,29]],"date-time":"2026-10-29T20:17:14Z","timestamp":1793305034842,"version":"4.5.0"},"reference-count":111,"publisher":"Wiley","issue":"9","license":[{"start":{"date-parts":[[2015,1,19]],"date-time":"2015-01-19T00:00:00Z","timestamp":1421625600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2015,2,23]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>An experimental and theoretical study of the first compound featuring a Si\uf8feP bond to a two\u2010coordinate silicon atom is reported. The NHC\u2010stabilized phosphasilenylidene (IDipp)Si\uf8fePMes* (IDipp=1,3\u2010bis(2,6\u2010diisopropylphenyl)imidazolin\u20102\u2010ylidene, Mes*=2,4,6\u2010<jats:italic>t<\/jats:italic>Bu<jats:sub>3<\/jats:sub>C<jats:sub>6<\/jats:sub>H<jats:sub>2<\/jats:sub>) was prepared by SiMe<jats:sub>3<\/jats:sub>Cl elimination from SiCl<jats:sub>2<\/jats:sub>(IDipp) and LiP(Mes*)SiMe<jats:sub>3<\/jats:sub> and characterized by X\u2010ray crystallography, NMR spectroscopy, cyclic voltammetry, and UV\/Vis spectroscopy. It has a planar <jats:italic>trans<\/jats:italic>\u2010bent geometry with a short Si\uf8ffP distance of 2.1188(7)\u2005\u00c5 and acute bonding angles at Si (96.90(6)\u00b0) and P (95.38(6)\u00b0). The bonding parameters indicate the presence of a Si\uf8feP bond with a lone electron pair of high s\u2010character at Si and P, in agreement with natural bond orbital (NBO) analysis. Comparative cyclic voltammetric and UV\/Vis spectroscopic experiments of this compound, the disilicon(0) compound (IDipp)Si\uf8feSi(IDipp), and the diphosphene Mes*P\uf8fePMes* reveal, in combination with quantum chemical calculations, the isolobal relationship of the three double\u2010bond systems.<\/jats:p>","DOI":"10.1002\/anie.201411264","type":"journal-article","created":{"date-parts":[[2015,1,19]],"date-time":"2015-01-19T14:58:58Z","timestamp":1421679538000},"page":"2739-2744","source":"Crossref","is-referenced-by-count":72,"title":["Si\uf8feP Double Bonds: Experimental and Theoretical Study of an NHC\u2010Stabilized Phosphasilenylidene"],"prefix":"10.1002","volume":"54","author":[{"given":"Daniel","family":"Gei\u00df","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marius I.","family":"Arz","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Martin","family":"Stra\u00dfmann","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gregor","family":"Schnakenburg","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alexander 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Chem. Int. Ed. Engl."},{"key":"e_1_2_2_46_3","first-page":"807","volume":"95","year":"1983","journal-title":"Angew. Chem."},{"key":"e_1_2_2_47_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0277-5387(00)80933-X"},{"key":"e_1_2_2_48_2","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.67.1980"},{"key":"e_1_2_2_49_2","unstructured":"The synthesis and full characterization of1 including the solution and solid\u2010state NMR spectra cyclic voltammograms results of the quantum chemical calculations and comparisons of the experimental and the calculated UV\/Vis spectra of1 Si2(IDipp)2 and P2Mes*2are given in the Supporting Information."},{"key":"e_1_2_2_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja200462y"},{"key":"e_1_2_2_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/om3008184"},{"key":"e_1_2_2_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00405a054"},{"key":"e_1_2_2_53_2","unstructured":"A CSD survey (21.11.2014) gave 15 compounds with Si\uf8feP double bonds leading to a median and a mean Si\uf8feP bond length of 2.092\u2005\u00c5 and 2.093\u2005\u00c5 respectively."},{"key":"e_1_2_2_54_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp810119k"},{"key":"e_1_2_2_55_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200504145"},{"key":"e_1_2_2_55_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200504145"},{"key":"e_1_2_2_56_2","unstructured":"\u00a0"},{"key":"e_1_2_2_57_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00149a004"},{"key":"e_1_2_2_58_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198907511"},{"key":"e_1_2_2_58_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19891010631"},{"key":"e_1_2_2_59_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199110221"},{"key":"e_1_2_2_59_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19911030814"},{"key":"e_1_2_2_60_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00061a034"},{"key":"e_1_2_2_61_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39950000253"},{"key":"e_1_2_2_62_2","doi-asserted-by":"publisher","DOI":"10.1016\/0010-8545(95)09102-5"},{"key":"e_1_2_2_63_2","doi-asserted-by":"publisher","DOI":"10.1021\/om9508851"},{"key":"e_1_2_2_64_2","doi-asserted-by":"publisher","DOI":"10.1039\/b710888e"},{"key":"e_1_2_2_65_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199713261"},{"key":"e_1_2_2_65_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19971091225"},{"key":"e_1_2_2_66_2","doi-asserted-by":"publisher","DOI":"10.1021\/om900310u"},{"key":"e_1_2_2_67_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9051153"},{"key":"e_1_2_2_68_2","doi-asserted-by":"publisher","DOI":"10.1021\/om2003442"},{"key":"e_1_2_2_69_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja4072699"},{"key":"e_1_2_2_70_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201308525"},{"key":"e_1_2_2_70_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201308525"},{"key":"e_1_2_2_71_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr940303"},{"key":"e_1_2_2_72_2","unstructured":"The31P\u2005NMR chemical shifts of phosphasilenes (R2Si\uf8fePR) depend strongly on the P\u2010substituent and range from \u221233\u2005ppm (Ref.\u2005[28i]) to +389.3\u2005ppm (Ref.\u2005[28j]). Interestingly the ylidic phosphasilene LSi\uf8fePH (L=CH(C\uf8feCH2)CMe(NDipp)2) shows an exceptional shielded31P\u2005NMR signal at\u03b4=\u2212293.9\u2005ppm (1J(P Si)=186.4\u2005Hz) (Ref.\u2005[28m])."},{"key":"e_1_2_2_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/om701038p"},{"key":"e_1_2_2_74_2","doi-asserted-by":"publisher","DOI":"10.1016\/0926-2040(93)90010-K"},{"key":"e_1_2_2_75_2","unstructured":"Selected references:"},{"key":"e_1_2_2_76_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00257a080"},{"key":"e_1_2_2_77_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00215a003"},{"key":"e_1_2_2_78_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00095a041"},{"key":"e_1_2_2_79_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja963921b"},{"key":"e_1_2_2_80_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja003389z"},{"key":"e_1_2_2_81_2","doi-asserted-by":"publisher","DOI":"10.1139\/v07-069"},{"key":"e_1_2_2_82_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201300461"},{"key":"e_1_2_2_82_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201300461"},{"key":"e_1_2_2_83_2","unstructured":"Both fragments have a triplet ground state with a ZPVE corrected singlet\u2013triplet gap of \u221256.3\u2005kJ\u2009mol\u22121(PMes*) and \u221230.6\u2005kJ\u2009mol\u22121(Si(IDipp)) calculated at the B3LYP\/6\u2010311G** level of theory."},{"key":"e_1_2_2_84_2","unstructured":"\u00a0"},{"key":"e_1_2_2_85_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0225774"},{"key":"e_1_2_2_86_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic060438l"},{"key":"e_1_2_2_87_2","unstructured":"Oxidation of1by [Fe(C5Me5)2]B(ArF)4(ArF=2 4 6\u2010(CF3)3C6H2) occurs rapidly in fluorobenzene at \u221240\u2009\u00b0C. Attempts to isolate the radical salt [(IDipp)Si\uf8fePMes*]B(ArF)4were unsuccessful owing to its thermolability. In comparison the green radical salt [Si2(IDipp)2]B(ArF)4was isolated and fully characterized: \u201cThe Reactivity of Molecular Disilicon(0)\u201d: A.\u2005C. Filippou O. Schiemann M. Stra\u00dfmann A. Meyer G. Schnakenburg M.\u2005I. Arz The 17th International Symposium on Silicon Chemistry (ISOS XVII) Berlin 3\u20138 August2014."},{"key":"e_1_2_2_88_2","unstructured":"P2Mes*2also undergoes a reversible one\u2010electron reduction atE1\/2=\u22121836\u2005mV in full agreement with previous reports which have shown that the radical anion [P2Mes*2]\u2212can be generated chemically and by bulk coulometry in THF solution:"},{"key":"e_1_2_2_89_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39820000691"},{"key":"e_1_2_2_90_2","doi-asserted-by":"publisher","DOI":"10.1039\/DT9870000249"},{"key":"e_1_2_2_91_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp991381"},{"key":"e_1_2_2_92_2","unstructured":"The UV\/Vis spectrum of the diphosphene P2Mes*2was reported in CH2Cl2and analyzed by quantum theory. The results compare well with those described herein:"},{"key":"e_1_2_2_93_2","unstructured":"see Ref.\u2005[26];"},{"key":"e_1_2_2_94_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja900813v"},{"key":"e_1_2_2_95_2","unstructured":"CCDC\u20051037826 contains the supplementary crystallographic data for this paper. 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