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Reacting various combinations of the pnictogenylboranes H<jats:sub>2<\/jats:sub>E\u2032\u2212BH<jats:sub>2<\/jats:sub>\u2212NMe<jats:sub>3<\/jats:sub> (E\u2032=P, As) with pnictogen\u2010based nucleophiles MER1R2 (E=P, As; R1=H, R2=<jats:sup><jats:italic>t<\/jats:italic><\/jats:sup>Bu; R1=R2=Ph; M=Na, K) allows for the isolation of the unsymmetrical products [Na(18\u2010crown\u20106)][H<jats:sub>2<\/jats:sub>E\u2032\u2212BH<jats:sub>2<\/jats:sub>\u2212EH<jats:sup>t<\/jats:sup>Bu] (<jats:bold>3<\/jats:bold>: E=E\u2032=P; <jats:bold>4<\/jats:bold>: E=E\u2032=As; <jats:bold>5<\/jats:bold>: E=As, E\u2032=P) and [M(C)][H<jats:sub>2<\/jats:sub>E\u2032\u2212BH<jats:sub>2<\/jats:sub>\u2212EPh<jats:sub>2<\/jats:sub>] (<jats:bold>7<\/jats:bold>: E=E\u2032=P, M=Na, C=18\u2010crown\u20106; <jats:bold>8<\/jats:bold>: E=E\u2032=As; M=K, C=[2.2.2]cryptand; <jats:bold>9<\/jats:bold>: E=P, E\u2032=As, M=Na, C=[2.2.2]cryptand; <jats:bold>10<\/jats:bold>: E=As, E\u2032=P, M=K, C=[2.2.2]cryptand). [Na(18\u2010crown\u20106)][H<jats:sub>2<\/jats:sub>As\u2212BH<jats:sub>2<\/jats:sub>\u2010<jats:sup>t<\/jats:sup>BuPH\u2212BH<jats:sub>3<\/jats:sub>] (<jats:bold>6<\/jats:bold>) is only accessible by a different pathway, using <jats:sup>t<\/jats:sup>BuPH<jats:sub>2<\/jats:sub>, BH<jats:sub>3<\/jats:sub>\u2009\u22c5\u2009SMe<jats:sub>2<\/jats:sub> and NaNH<jats:sub>2<\/jats:sub> as starting materials. Additionally, the synthesis of symmetrical diphenyl\u2010substituted compounds [M(18\u2010crown\u20106)][Ph<jats:sub>2<\/jats:sub>E\u2212BH<jats:sub>2<\/jats:sub>\u2212EPh<jats:sub>2<\/jats:sub>] (<jats:bold>11<\/jats:bold>: E=P, M=Na; <jats:bold>12<\/jats:bold>: E=As, M=K) is reported which can be regarded as isostructural inorganic, negatively charged analogs of dppm (1,1\u2010bis(diphenylphosphino)methane) and dpam (1,1\u2010bis(diphenylarsino)methane). Furthermore, an elongation of the pnictogen boron backbone in compounds <jats:bold>3<\/jats:bold>, <jats:bold>7<\/jats:bold> and <jats:bold>9<\/jats:bold>\u2032 (similar compound to <jats:bold>9<\/jats:bold>, stabilized however by 18\u2010crown\u20106), is attainable by reacting them with the pnictogenylboranes H<jats:sub>2<\/jats:sub>E\u2032\u2212BH<jats:sub>2<\/jats:sub>\u2212NMe<jats:sub>3<\/jats:sub> leading to corresponding five\u2010membered chain\u2010like compounds [Na(18\u2010crown\u20106)][H<jats:sub>2<\/jats:sub>E\u2212BH<jats:sub>2<\/jats:sub>\u2212R1R2P\u2212BH<jats:sub>2<\/jats:sub>\u2212E\u2032H<jats:sub>2<\/jats:sub>] (E=E\u2032=P, R1=H, R2=<jats:sup><jats:italic>t<\/jats:italic><\/jats:sup>Bu (<jats:bold>13<\/jats:bold>); E=E\u2032=P, R1=R2=Ph (<jats:bold>14<\/jats:bold>); E=E\u2032=As, R1=R2=Ph (<jats:bold>15<\/jats:bold>); E=P, E\u2032=As, R1=R2=Ph (<jats:bold>16<\/jats:bold>)). Finally, the thermodynamics of the reaction pathways were evaluated by quantum chemical computations.<\/jats:p>","DOI":"10.1002\/chem.202203206","type":"journal-article","created":{"date-parts":[[2022,12,7]],"date-time":"2022-12-07T11:01:10Z","timestamp":1670410870000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Three\u2010 and Five\u2010Membered Anionic Chains of Pnictogenylboranes"],"prefix":"10.1002","volume":"29","author":[{"given":"Mehdi Elsayed","family":"Moussa","sequence":"first","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie der Universit\u00e4t Regensburg  93040 Regensburg Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Tobias","family":"Kahoun","sequence":"additional","affiliation":[{"name":"Institut f\u00fcr Anorganische Chemie der Universit\u00e4t Regensburg  93040 Regensburg 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Thus a glass-coated stirring bar is used instead. As a side product the formation of Na[H3B\u2212tBuPH\u2212BH3]\u2212is detected."},{"key":"e_1_2_8_77_1","unstructured":"Compounds5and6are partially contaminated with impurities ([H2PBH2PH2]\u2212and [H3P\u2212tBuPH\u2212BH3]\u2212 respectively) of 10 to 15\u2009% depending on the sample. Due to similar solubilities of each of5and6with their associated impurities crystals of these impurities were also found with those of5and6. Under the microscope it is visually possible to distinguish crystals of5or6from their impurities and thus we were able to separate (in a glove box) few pure milligrams of each of them necessary for EA. 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