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Variable\u2010temperature solution and solid\u2010state <jats:sup>31<\/jats:sup>P\u2005NMR spectroscopy measurements were performed and X\u2010ray diffraction studies revealed an \u03b7<jats:sup>2<\/jats:sup>:\u03b7<jats:sup>1<\/jats:sup> coordination mode for the Mo<jats:sub>2<\/jats:sub>P<jats:sub>2<\/jats:sub> unit of <jats:bold>2<\/jats:bold> in the Cu<jats:sup>I<\/jats:sup> bimetallic complexes <jats:bold>3<\/jats:bold> and <jats:bold>4<\/jats:bold>. DFT calculations were carried out to highlight the bonding situation of this unprecedented coordination mode in the Cu<jats:sup>I<\/jats:sup> bimetallic compound <jats:bold>3<\/jats:bold>. It is built up from a side\u2010on coordination of the P\uf8ffP \u03c3 bond to one copper ion and from the interaction of the lone pair of one phosphorus atom with the second copper ion. The remaining available lone pair of the second phosphorus atom can be involved as well to interact with an additional metal centre, as evidenced in the Cu<jats:sup>I<\/jats:sup> trimetallic compound <jats:bold>5<\/jats:bold> in which an \u03b7<jats:sup>2<\/jats:sup>:\u03b7<jats:sup>1<\/jats:sup>:\u03b7<jats:sup>1<\/jats:sup> coordination mode of the ligand <jats:bold>2<\/jats:bold> is observed. Derivative <jats:bold>3<\/jats:bold> can be used as a molecular clip to obtain discrete \u03c0\u2010stacked dimers through a ligand exchange reaction between acetonitrile ligands and cyano\u2010capped \u03c0\u2010conjugated systems, indicating the stability of the new \u03b7<jats:sup>2<\/jats:sup>:\u03b7<jats:sup>1<\/jats:sup> coordination mode.<\/jats:p>","DOI":"10.1002\/chem.201100845","type":"journal-article","created":{"date-parts":[[2011,7,1]],"date-time":"2011-07-01T12:03:07Z","timestamp":1309521787000},"page":"9130-9141","source":"Crossref","is-referenced-by-count":21,"title":["Simultaneous End\u2010On\/Side\u2010On Coordination Modes of a Diphosphorus Tetrahedral Complex Imposed by Pre\u2010organization of Oligometallic Cu<sup>I<\/sup> Acceptors"],"prefix":"10.1002","volume":"17","author":[{"given":"Stefan","family":"Welsch","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Christophe","family":"Lescop","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Gabor","family":"Balazs","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"R\u00e9gis","family":"R\u00e9au","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Manfred","family":"Scheer","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2011,7]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"For recent reviews see:"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr100010e"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900349u"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr9003709"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/b718179p"},{"key":"e_1_2_6_6_2","unstructured":"\u00a0"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/om9806794"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00263a010"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19820940503"},{"key":"e_1_2_6_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198203301"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01048a035"},{"key":"e_1_2_6_11_2","unstructured":"\u00a0"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39860001799"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1002\/asia.200900309"},{"key":"e_1_2_6_14_2","unstructured":"\u00a0"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1521-3765(19981002)4:10<1917::AID-CHEM1917>3.0.CO;2-9"},{"key":"e_1_2_6_16_2","unstructured":"J. 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