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First the chloride complexes [{CH(PPh<jats:sub>2<\/jats:sub>NSiMe<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>}Ln{(Ph<jats:sub>2<\/jats:sub>P)<jats:sub>2<\/jats:sub>N}Cl] (Ln=Y (<jats:bold>1\u2009a<\/jats:bold>), La (<jats:bold>1\u2009b<\/jats:bold>), Nd (<jats:bold>1\u2009c<\/jats:bold>), Yb (<jats:bold>1\u2009d<\/jats:bold>)) having the bulky [CH(PPh<jats:sub>2<\/jats:sub>NSiMe<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> and the flexible [(Ph<jats:sub>2<\/jats:sub>P)<jats:sub>2<\/jats:sub>N]<jats:sup>\u2212<\/jats:sup> ligands in the same molecule were prepared by three different synthetic pathways. Compounds <jats:bold>1\u2009a<\/jats:bold>\u2013<jats:bold>d<\/jats:bold> can be obtained by reaction of [{[CH(PPh<jats:sub>2<\/jats:sub>NSiMe<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>]LnCl<jats:sub>2<\/jats:sub>}<jats:sub>2<\/jats:sub>] with [K(thf)<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub>N(PPh<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>] (<jats:italic>n<\/jats:italic>=1.25, 1.5) or by treatment of [{(Ph<jats:sub>2<\/jats:sub>P)<jats:sub>2<\/jats:sub>N}LnCl<jats:sub>2<\/jats:sub>(thf)<jats:sub>3<\/jats:sub>] with K[CH(PPh<jats:sub>2<\/jats:sub>NSiMe<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>]. Furthermore, a one\u2010pot reaction of K[CH(PPh<jats:sub>2<\/jats:sub>NSiMe<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>] with LnCl<jats:sub>3<\/jats:sub> and [K(thf)<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub>N(PPh<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>] leads to the same products. Single\u2010crystal X\u2010ray structures of <jats:bold>1\u2009a<\/jats:bold>\u2013<jats:bold>d<\/jats:bold> show that the conformation of the six\u2010membered metallacycle (N1\u2010P1\u2010C1\u2010P2\u2010N2\u2010Ln) which is formed by chelation of the [CH(PPh<jats:sub>2<\/jats:sub>NSiMe<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> ligand to the lanthanide atom is influenced by the ionic radius of the central metal atom. In solution dynamic behavior of the [(Ph<jats:sub>2<\/jats:sub>P)<jats:sub>2<\/jats:sub>N]<jats:sup>\u2212<\/jats:sup> ligand is observed, which is caused by rapid exchange of the two different phosphorus atoms. Further reaction of <jats:bold>1\u2009b<\/jats:bold> with KNPh<jats:sub>2<\/jats:sub> resulted in [{(Me<jats:sub>3<\/jats:sub>SiNPPh<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>CH}La{N(PPh<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>}(NPh<jats:sub>2<\/jats:sub>)] (<jats:bold>2<\/jats:bold>). Compounds <jats:bold>1\u2009a<\/jats:bold>\u2013<jats:bold>d<\/jats:bold> and <jats:bold>2<\/jats:bold> are active in the ring\u2010opening polymerization of \u03b5\u2010caprolactone and the polymerization of methyl methacrylate. In some cases high molecular weight polymers with good conversions and narrow polydispersities were obtained. In both polymerizations the catalytic activity depends on the ionic radius of the metal center.<\/jats:p>","DOI":"10.1002\/chem.200401062","type":"journal-article","created":{"date-parts":[[2005,3,18]],"date-time":"2005-03-18T10:01:30Z","timestamp":1111140090000},"page":"3165-3172","source":"Crossref","is-referenced-by-count":83,"title":["Yttrium and Lanthanide Complexes with Various P,N Ligands in the Coordination Sphere: Synthesis, Structure, and Polymerization Studies"],"prefix":"10.1002","volume":"11","author":[{"given":"Michael T.","family":"Gamer","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marcus","family":"Rast\u00e4tter","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Peter W.","family":"Roesky","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alexandra","family":"Steffens","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mario","family":"Glanz","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2005,4,28]]},"reference":[{"key":"e_1_2_6_1_2","first-page":"256","volume-title":"Lanthanides: Chemistry and Use in Organic Chemistry","author":"Kobayashi S.","year":"1999"},{"key":"e_1_2_6_2_2","unstructured":"\u00a0"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00038a069"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma00078a004"},{"key":"e_1_2_6_5_2","unstructured":"\u00a0"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma00101a044"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma00127a040"},{"key":"e_1_2_6_8_2","unstructured":"\u00a0"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(98)00751-7"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(98)00977-2"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/om990952h"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma000679r"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3749(200012)626:12<2467::AID-ZAAC2467>3.0.CO;2-I"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1351\/pac200173020279"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0301334"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/om030454f"},{"key":"e_1_2_6_17_2","unstructured":"\u00a0"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ma951400n"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/om9705867"},{"key":"e_1_2_6_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/om0499097"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200400319"},{"key":"e_1_2_6_22_2","unstructured":"\u00a0"},{"key":"e_1_2_6_23_2","first-page":"174","volume":"33","author":"McLain S. 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