{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,2,7]],"date-time":"2026-02-07T02:47:33Z","timestamp":1770432453906,"version":"3.49.0"},"reference-count":157,"publisher":"Wiley","issue":"1","license":[{"start":{"date-parts":[[2007,9,26]],"date-time":"2007-09-26T00:00:00Z","timestamp":1190764800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2008,1]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Reactions of imido complexes [M(Cp)(\uf8feNR\u2032)(PR\u2032\u2032<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>] (M=V, Nb) with silanes afford a plethora of products, depending on the nature of the metal, substitution at silicon and nitrogen and the steric properties of the phosphine. The main products are [M(Cp)(\uf8feNR\u2032)(PR<jats:sub>3<\/jats:sub>)(H)(SiR<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub>Cl<jats:sub>3\u2212<jats:italic>n<\/jats:italic><\/jats:sub>)] (M=V, Nb; R\u2032=2,6\u2010diisopropylphenyl (Ar), 2,6\u2010dimethylphenyl (Ar\u2032)), [Nb(Cp)(\uf8feNR\u2032)(PR\u2032\u2032<jats:sub>3<\/jats:sub>)(H)(SiPhR<jats:sub>2<\/jats:sub>)] (R<jats:sub>2<\/jats:sub>=MeH, H<jats:sub>2<\/jats:sub>), [Nb(Cp)(\uf8feNR\u2032)(PR\u2032\u2032<jats:sub>3<\/jats:sub>)(Cl)(SiHR<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub>Cl<jats:sub>2\u2212<jats:italic>n<\/jats:italic><\/jats:sub>)] and [Nb(Cp)(\u03b7<jats:sup>3<\/jats:sup>\u2010N(R)SiR<jats:sub>2<\/jats:sub>\uf8ffH\u22c5\u22c5\u22c5)(PR\u2032\u2032<jats:sub>3<\/jats:sub>)(Cl)]. Complexes with the smaller Ar\u2032 substituent at nitrogen react faster, as do more acidic silanes. Bulkier groups at silicon and phosphorus slow down the reaction substantially. Kinetic NMR experiments supported by DFT calculations reveal an associative mechanism going via an intermediate N\u2010silane adduct [Nb(Cp){\uf8feN(\u2192SiHClR<jats:sub>2<\/jats:sub>)R\u2032}(PR\u2032\u2032<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>] bearing a penta\u2010coordinate silicon centre, which then rearranges into the final products through a Si\uf8ffH or Si\uf8ffCl bond activation process. DFT calculations show that this imido\u2010silane adduct is additionally stabilized by a Si\uf8ffH\u22c5\u22c5\u22c5M agostic interaction. Si\uf8ffH activation is kinetically preferred even when Si\uf8ffCl activation affords thermodynamically more stable products. The niobium complexes [NbCp(\uf8feNAr)(PMe<jats:sub>3<\/jats:sub>)(H)(SiR<jats:sub>2<\/jats:sub>Cl)] (R=Ph, Cl) are classical according to X\u2010ray studies, but DFT calculations suggest the presence of interligand hypervalent interactions (IHI) in the model complex [Nb(Cp) (\uf8feNMe)(PMe<jats:sub>3<\/jats:sub>)(H)(SiMe<jats:sub>2<\/jats:sub>Cl)]. The extent of Si\uf8ffH activation in the \u03b2\u2010Si\uf8ffH\u22c5\u22c5\u22c5M agostic complexes [Cp{\u03b7<jats:sup>3<\/jats:sup>\u2010N(R\u2032)SiR<jats:sub>2<\/jats:sub>\uf8ffH\u22c5\u22c5\u22c5}M(PR\u2032\u2032<jats:sub>3<\/jats:sub>)(Cl)] (R\u2032\u2032=PMe<jats:sub>3<\/jats:sub>, PMe<jats:sub>2<\/jats:sub>Ph) primarily depends on the identity of the ligand <jats:italic>trans<\/jats:italic> to the Si\uf8ffH bond. A <jats:italic>trans<\/jats:italic> phosphine leads to a stronger Si\uf8ffH bond, manifested by a larger <jats:italic>J<\/jats:italic>(Si\uf8ffH) coupling constant. The Si\uf8ffH activation diminishes slightly when a less basic phosphine is employed, consistent with decreased back\u2010donation from the metal.<\/jats:p>","DOI":"10.1002\/chem.200700271","type":"journal-article","created":{"date-parts":[[2007,9,26]],"date-time":"2007-09-26T10:19:50Z","timestamp":1190801990000},"page":"296-310","source":"Crossref","is-referenced-by-count":32,"title":["Non\u2010Innocent Behaviour of Imido Ligands in the Reactions of Silanes with Half\u2010Sandwich Imido Complexes of Nb and V: A Silane\/Imido Coupling Route to Compounds with Nonclassical Si\uf8ffH Interactions"],"prefix":"10.1002","volume":"14","author":[{"given":"Stanislav\u2005K.","family":"Ignatov","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Nicholas\u2005H.","family":"Rees","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Alexei\u2005A.","family":"Merkoulov","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Stuart\u2005R.","family":"Dubberley","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Alexei\u2005G.","family":"Razuvaev","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Philip","family":"Mountford","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Georgii\u2005I.","family":"Nikonov","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2007,12,17]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00174a052"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00060a045"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/dt9920000739"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00035a047"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19941061216"},{"key":"e_1_2_6_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199412551"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/DT9940001607"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470166437.ch4"},{"key":"e_1_2_6_9_2","unstructured":"\u00a0"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3757(19990215)111:4<448::AID-ANGE448>3.0.CO;2-2"},{"key":"e_1_2_6_10_3","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3773(19990215)38:4<428::AID-ANIE428>3.0.CO;2-3"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr980461r"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.200404267"},{"key":"e_1_2_6_13_2","unstructured":"\u00a0"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/om030567z"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic030282e"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/om020509y"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0203227"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(01)01386-9"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/om970527t"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9721982"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20010302)7:5<945::AID-CHEM945>3.0.CO;2-3"},{"key":"e_1_2_6_22_2","unstructured":"\u00a0"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0020-1693(02)01271-9"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/om000503d"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/om960813p"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00084a077"},{"key":"e_1_2_6_27_2","unstructured":"for 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However we found a transition stateTS\u203222\u201319with the structural characteristics of a \u03b71\u2010silane complex having electronic energy of 27.1\u2005kcal\u2009mol\u22121(\u0394G=24.0\u2005kcal\u2009mol\u22121) which is below the energy of the pair22+HSiClMe2. This suggests that the initial attack of HSiClMe2on22most likely goes via a \u03b71\u2010silane intermediate Cp(MeN=)Nb(PMe3)(\u03b71\u2010HSiClMe2) which then rearranges via theTS\u203222\u201319to complex19."},{"key":"e_1_2_6_141_2","doi-asserted-by":"publisher","DOI":"10.1021\/om050703v"},{"key":"e_1_2_6_142_2","first-page":"31","volume":"8","author":"Allen F. H.","year":"1993","journal-title":"Chem. Des. Autom. News"},{"key":"e_1_2_6_143_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0065-3055(08)60501-8"},{"key":"e_1_2_6_144_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200401104"},{"key":"e_1_2_6_145_2","doi-asserted-by":"publisher","DOI":"10.1002\/1099-0682(200111)2001:11<2947::AID-EJIC2947>3.0.CO;2-#"},{"key":"e_1_2_6_146_2","unstructured":"Silane \u03c3\u2010bond metathesis reactions on imido complexes have been intensively studied by Tilley and co\u2010workers: ref.\u2005[3a b d e\u2013g]."},{"key":"e_1_2_6_147_2","unstructured":"J.\u2005A. Pople et\u2005al.; Gaussian 03 Revision C.02 Gaussian Inc.: Wallingford CT 2004. The full reference is in theSupporting Information."},{"key":"e_1_2_6_148_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.464913"},{"key":"e_1_2_6_149_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.54.16533"},{"key":"e_1_2_6_150_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.448975"},{"key":"e_1_2_6_151_2","unstructured":"\u00a0"},{"key":"e_1_2_6_152_2","unstructured":"SHELXTL\u2010Plus Release 5.10 Bruker AXS Inc. Madison Wisconsin (USA) 1997;"},{"key":"e_1_2_6_153_2","unstructured":"for complex3\u2009ethe program CRYSTALS has been used for structural refinement:D.\u2005J.Watkin C.\u2005K.Prout J.\u2005R.Carruthers P.\u2005W.Betteridge R.\u2005I.Cooper CRYSTALS issue 11 Chemical Crystallography Laboratory: Oxford UK 2001."},{"key":"e_1_2_6_154_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2006.08.065"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.200700271","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200700271","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T14:03:31Z","timestamp":1760277811000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.200700271"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2007,12,17]]},"references-count":157,"journal-issue":{"issue":"1","published-print":{"date-parts":[[2008,1]]}},"alternative-id":["10.1002\/chem.200700271"],"URL":"https:\/\/doi.org\/10.1002\/chem.200700271","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2007,12,17]]}}}