The Variable Binding Modes of Phenylbis(pyrid‐2‐ylmethyl)phosphane and Bis(pyrid‐2‐ylmethyl) Phenylphosphonite with Ag^I and Cu^I

Abstract

A series of new bridging phosphane and phosphonite structures forming three‐ and six‐membered rings with the metal centers were synthesized and characterized. The resulting compounds of phenylbis(pyrid‐2‐ylmethyl)phosphane (1) with the silver(I) salts of trifluoroacetate (tfa–), tetrafluoroborate (BF4–), and trifluoromethanesulfonate (OTf–), and copper tetrakis(acetonitrile) hexafluorophosphate (PF6–) shows the flexibility of the ligand by displaying different coordination modes associated with the electronic and structural characteristics of the corresponding anion. Accordingly, ligand 1 in these complexes displays two different binding modes. With Agtfa and AgBF4 compounds 3 and 4 are obtained where the ligand chelates to two silver atoms that exhibit normalAg–Ag contacts in the range of 2.9 Å. When AgOTf or Cu(NCCH3)4PF6 are used, one molecule of 1 bridges the metal centers through a phosphorus atom while another is terminally bound. This induces short M–M distances of 2.6871 and 2.568 Å for 5 and 6, respectively. Similarly, the coordination behavior of the heterofunctional bis(pyrid‐2‐ylmethyl) phenylphosphonite ligand (2) is reported with Cu(NCCH3)4PF6 (7) and AgBF4 (8) to form two novel discrete molecules. In these complexes 2 coordinates through the P and N atoms, with the difference that in 7 the O atom of one of the carbinol arms is also bound to the Cu. Elemental analysis, variable‐temperature multinuclear NMR spectroscopy, single‐crystal X‐ray diffraction, and low‐temperature luminescence studies were carried out to fully characterize the compounds. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Coinage Metal Complexes of Bis(quinoline‐2‐ylmethyl)phenylphosphine‐Simple Reactions Can Lead to Unprecedented Results

“… [31] Both copper atoms are very close to each other (2.588(9) Å); regardless, the shortest Cu⋅⋅⋅Cu distance in a phosphine complex was reported for a copper(I) hexafluorophosphate complex salt of bis(pyridine‐2‐ylmethyl)phenylphosphine with 2.488(12) Å. [32] The close proximity and the resulting π‐stacking interactions of the phenyl rings as well as the quinaldinyl rings of the closed‐wings ligand probably allow for such close copper contacts (see also Figure S2 of the Supporting Information). Furthermore, the Cu1−P1 (2.527(2) Å) and Cu2−P1 distances are not equidistant and differ by 0.281 Å.…”

“… [30] The metal‐metal distances (Cu1⋅⋅⋅Cu2 2.451(1) Å and Cu3⋅⋅⋅Cu4 2.447(1) Å) in 2 are very short, even shorter than in the previously mentioned copper(I) hexafluorophosphate complex salt of bis(pyridine‐2‐ylmethyl)phenylphosphine. [32] The coordination of both ligands in 2 occurs in an open‐wing manner. The Cu1−P1 and Cu2‐P1 distances are very similar and only differ by 0.016 Å, whereas the Cu3−P2 and Cu4−P2 distances differ by 0.138 Å.…”

Methoxyphenyl Substituted Bis(picolyl)phosphines and Phosphine Oxides

“…The luminescence spectroscopic data were recorded, indicating luminescent properties. [10] The CH 2 -groups of 1 can be easily deprotonated with nBuLi or Sn{N(SiMe 3 ) 2 } 2 leading to corresponding complexes containing the dianion of the ligand. [11] Additionally, Pd II , Ir I and mixed Cr III /Tl I complexes with ligand 1 have been synthesized.…”

Bi- and trinuclear coinage metal complexes of a PNNP ligand featuring metallophilic interactions and an unusual charge separation

“…Ag-N and Ag-P bond distances are consistent with literature values, except for Ag1-P2, which is slightly elongated. 59,78,79 In the 31 P{ 1 H} NMR spectrum, a broad misshaped doublet at δ = −12.0 ppm ( n J = 385.8 Hz) is observed, indicating higher order coupling with the silver nuclei and/or through the P-Ag-P or P-Ag 3 -P chain. 61,62,80,81 In the 1 H NMR spectrum, the NCHN resonance was detected as a multiplet at δ = 7.61-7.52 ppm.…”