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The nature and bonding situations were studied with the NBO method and with the charge and energy decomposition analysis EDA\u2010NOCV. The addition of ethylene to Ph\n                    <jats:sub>2<\/jats:sub>\n                    N\uf8ffEE\uf8ffNPh\n                    <jats:sub>2<\/jats:sub>\n                    takes place through an initial [2+1] addition to one metal atom and consecutive rearrangement to four\u2010membered cyclic species, which feature a weak E\uf8ffE bond. Rotation about the C\uf8ffC bond with concomitant rupture of the E\uf8ffE bond leads to the 1,2\u2010disubstituted ethanes, which have terminal E(NPh\n                    <jats:sub>2<\/jats:sub>\n                    ) groups. The overall reaction Ph\n                    <jats:sub>2<\/jats:sub>\n                    N\uf8ffEE\uf8ffNPh\n                    <jats:sub>2<\/jats:sub>\n                    +C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    \u2192(Ph\n                    <jats:sub>2<\/jats:sub>\n                    N)E\uf8ffC\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    \uf8ffE(NPh\n                    <jats:sub>2<\/jats:sub>\n                    ) has very low activation barriers and is slightly exergonic for E=Ge but slightly endergonic for E=Sn. The analysis of the electronic structure shows that there is charge donation of nearly one electron to the ethylene moiety already in the first part of the reaction. The energy partitioning analysis suggests that the HOMO(Ph\n                    <jats:sub>2<\/jats:sub>\n                    N\uf8ffEE\uf8ffNPh\n                    <jats:sub>2<\/jats:sub>\n                    )\u2192LUMO(C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    ) interaction has a similar strength as the HOMO(C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    )\u2192LUMO(Ph\n                    <jats:sub>2<\/jats:sub>\n                    N\uf8ffEE\uf8ffNPh\n                    <jats:sub>2<\/jats:sub>\n                    ) interaction. The [2+2] addition of acetylene to Ph\n                    <jats:sub>2<\/jats:sub>\n                    N\uf8ffEE\uf8ffNPh\n                    <jats:sub>2<\/jats:sub>\n                    also takes place through an initial [2+1] approach, which eventually leads to 1,2\u2010disubstituted olefins (Ph\n                    <jats:sub>2<\/jats:sub>\n                    N)E\uf8ffC\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>2<\/jats:sub>\n                    \uf8ffE(NPh\n                    <jats:sub>2<\/jats:sub>\n                    ). The formation of the energetically lowest lying conformations of\n                    <jats:italic>cis<\/jats:italic>\n                    \u2010(Ph\n                    <jats:sub>2<\/jats:sub>\n                    N)E\uf8ffC\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>2<\/jats:sub>\n                    \uf8ffE(NPh\n                    <jats:sub>2<\/jats:sub>\n                    ), which occurs with very low activation barriers, is clearly exergonic for the germanium and the tin compound. The\n                    <jats:italic>trans<\/jats:italic>\n                    \u2010coordinated isomers of (Ph\n                    <jats:sub>2<\/jats:sub>\n                    N)E\uf8ffC\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>2<\/jats:sub>\n                    \uf8ffE(NPh\n                    <jats:sub>2<\/jats:sub>\n                    ) are slightly lower in energy than the\n                    <jats:italic>cis<\/jats:italic>\n                    form but they are separated by a substantial energy barrier for the rotation about the C\uf8ffC bond. The energy decomposition analysis indicates that the initial reaction takes place under formation of electron\u2010sharing bonds between triplet fragments rather than HOMO\u2013LUMO interactions.\n                  <\/jats:p>","DOI":"10.1002\/chem.201501457","type":"journal-article","created":{"date-parts":[[2015,7,19]],"date-time":"2015-07-19T15:03:06Z","timestamp":1437318186000},"page":"12405-12413","source":"Crossref","is-referenced-by-count":25,"title":["Reaction Mechanism of the Symmetry\u2010Forbidden [2+2] Addition of Ethylene and Acetylene to Amido\u2010Substituted Digermynes and Distannynes Ph\n                    <sub>2<\/sub>\n                    N\uf8ffEE\uf8ffNPh\n                    <sub>2<\/sub>\n                    , (E=Ge, Sn): A Theoretical Study"],"prefix":"10.1002","volume":"21","author":[{"given":"Lili","family":"Zhao","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Cameron","family":"Jones","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gernot","family":"Frenking","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2015,7,16]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"\u00a0"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar2000875"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1038\/nature08634"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/tcr.201100016"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja993346m"},{"key":"e_1_2_6_6_2","unstructured":"\u00a0"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.66.413"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.463421"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp020219v"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp025763i"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp0204814"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja029862l"},{"key":"e_1_2_6_13_2","unstructured":"\u00a0"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020517)41:10<1785::AID-ANIE1785>3.0.CO;2-6"},{"key":"e_1_2_6_14_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20020517)114:10<1863::AID-ANGE1863>3.0.CO;2-I"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1102209"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/aoc.824"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/om700365p"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9108566"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201308517"},{"key":"e_1_2_6_19_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201308517"},{"key":"e_1_2_6_20_2","unstructured":"\u00a0"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00315a024"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/qua.560250310"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(84)87036-0"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.450462"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(87)80398-6"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100313a025"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100338a027"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1021\/j100377a036"},{"key":"e_1_2_6_29_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.463422"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1016\/0009-2614(90)85439-J"},{"key":"e_1_2_6_31_2","first-page":"125","volume-title":"Advanced Organometallic Chemistry Vol.\u200533","author":"Grev R. 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