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The nature of the metal\u2010CO interactions and the relativistic effects on the different energy terms were analyzed with the EDA\u2010NOCV method. The three terms Pauli repulsion, Coulomb attraction, and orbital interactions become stronger when relativistic effects are accounted for; the strengthening exhibits the order \u0394<jats:italic>E<\/jats:italic><jats:sub>Pauli<\/jats:sub>&gt;\u0394<jats:italic>E<\/jats:italic><jats:sub>elstat<\/jats:sub>&gt;\u0394<jats:italic>E<\/jats:italic><jats:sub>orb<\/jats:sub>. The largest change in the calculated energy terms is, as expected, found for gold, followed by silver and copper. The relativistic contributions on the Cu<jats:sup>+<\/jats:sup>\u2010CO interactions are significant and thus, relativistic effects should not be neglected in quantum chemical calculations in copper compounds. Breakdown of the orbital term into individual contributions shows that the relativistic effect in [TM(CO)]<jats:sup>+<\/jats:sup> is for the TM<jats:sup>+<\/jats:sup>\u2190CO \u03c3\u2010donation stronger than for TM<jats:sup>+<\/jats:sup>\u2192CO \u03c0\u2010backdonation, except for TM=Cu. The trend in the dicarbonyls [TM(CO)<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup> has the order (+,+) \u03c3\u2010donation &gt; \u03c0\u2010backdonation &gt; (+,\u2212) \u03c3\u2010donation. The bonding analysis reveals that there is a sizeable contribution from TM<jats:sup>+<\/jats:sup>\u2192CO \u03c3\u2010backdonation in all carbonyl complexes that further stabilizes the metal\u2010carbonyl bonds. In [Au(CO)<jats:sub>2<\/jats:sub>]<jats:sup>+<\/jats:sup> it becomes even larger than the (+,\u2212) OC\u2192TM<jats:sup>+<\/jats:sup>\u2190CO \u03c3\u2010donation. The trends of the various orbital interactions and the effect of relativity on their strength can be understood when the valence orbitals of the metals and CO are considered.<\/jats:p>","DOI":"10.1002\/chem.201801410","type":"journal-article","created":{"date-parts":[[2018,5,2]],"date-time":"2018-05-02T10:55:11Z","timestamp":1525258511000},"page":"11675-11682","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":23,"title":["Relativistic Effects on Donor\u2013Acceptor Interactions in Coinage Metal Carbonyl Complexes [TM(CO)<sub><i>n<\/i><\/sub>]<sup>+<\/sup> (TM=Cu, Ag, Au; <i>n<\/i>=1, 2)"],"prefix":"10.1002","volume":"24","author":[{"given":"Christina","family":"Poggel","sequence":"first","affiliation":[{"name":"Fachbereich Chemie Philipps-Universit\u00e4t Marburg  Hans-Meerwein-Stra\u00dfe 35043 Marburg Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1689-1197","authenticated-orcid":false,"given":"Gernot","family":"Frenking","sequence":"additional","affiliation":[{"name":"Fachbereich Chemie Philipps-Universit\u00e4t Marburg  Hans-Meerwein-Stra\u00dfe 35043 Marburg Germany"},{"name":"Institute of Advanced Synthesis Nanjing Tech University  211816 Nanjing China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2018,7,10]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","first-page":"79","volume":"18","author":"Dewar M. 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