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Herein, we depict the reactivity studies of the bis\u2010cAAC\u2010stabilized di\u2010phosphorus (P<jats:sub>2<\/jats:sub>) having an inversely polarized phosphaalkene nature featuring the C=P double bonds with Au(I)Cl. Both the mono\u2010, and the di\u2010aurated phosphaalkenes with the formulae [(Me<jats:sub>2<\/jats:sub>\u2010cAAC=P)<jats:sub>2<\/jats:sub>(AuCl)] (<jats:bold>2<\/jats:bold>), and [(Me<jats:sub>2<\/jats:sub>\u2010cAAC=P)<jats:sub>2<\/jats:sub>(AuCl)<jats:sub>2<\/jats:sub>] (<jats:bold>3<\/jats:bold>), respectively have been isolated in the solid state. Moreover, for the first time, we have been able to isolate the cAAC\u2010stabilized tetra\u2010aurated elusive di\u2010phosphorus\u2010monoxide (P<jats:sub>2<\/jats:sub>O) with the formula [(Cy\u2010cAAC=P)\u2212O\u2212(P=cAAC\u2212Cy)(AuCl)<jats:sub>4<\/jats:sub>] (<jats:bold>5<\/jats:bold>) in presence of oxygen. Complexes <jats:bold>2\u20133<\/jats:bold>, <jats:bold>5<\/jats:bold> have been structurally characterized by single crystal X\u2010ray diffraction, and further studied by NMR spectroscopy. Our findings reveal significant elongation of the C<jats:sub>cAAC<\/jats:sub>\u2212P bonds in <jats:bold>2<\/jats:bold>\u2013<jats:bold>3<\/jats:bold>, <jats:bold>5<\/jats:bold>, and the presence of aurophilic interaction in <jats:bold>5<\/jats:bold>. Quantum chemical calculations, including density functional theory (DFT), and energy decomposition analysis coupled with natural orbitals for chemical valence (EDA\u2010NOCV) have been performed to study the electron densities distribution and nature of bonding in <jats:bold>2<\/jats:bold>\u2013<jats:bold>3<\/jats:bold>, <jats:bold>5<\/jats:bold>.<\/jats:p>","DOI":"10.1002\/asia.202300882","type":"journal-article","created":{"date-parts":[[2023,11,27]],"date-time":"2023-11-27T18:54:46Z","timestamp":1701111286000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Coordination Chemistry of Bis\u2010Cyclic Alkyl(Amino) Carbene (cAAC)\u2010Supported Di\u2010Phosphorus (P<sub>2<\/sub>): An Efficient Route to Donor Base\u2010Stabilized Elusive Di\u2010Phosphorus\u2010Monoxide(P<sub>2<\/sub>O)\u2010Gold Complex"],"prefix":"10.1002","volume":"19","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0506-4885","authenticated-orcid":false,"given":"Maria","family":"Francis","sequence":"first","affiliation":[{"name":"Department of Chemistry Indian Institute of Science Education and Research (IISER) Tirupati  Tirupati 517507 India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4490-4207","authenticated-orcid":false,"given":"Ekta","family":"Nag","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Science Education and Research (IISER) Tirupati  Tirupati 517507 India"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5883-4329","authenticated-orcid":false,"given":"Sudipta","family":"Roy","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Science Education and Research (IISER) Tirupati  Tirupati 517507 India"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2023,12,8]]},"reference":[{"key":"e_1_2_10_1_1","unstructured":"\u00a0"},{"key":"e_1_2_10_2_2","unstructured":"M.\u2005W. 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