cyclo‐P₄ Building Blocks: Achieving Non‐Classical Fullerene Topology and Beyond

Abstract

The cyclo‐P4 complexes [CpRTa(CO)2(η4‐P4)] (CpR: Cp′′=1,3‐C5H3tBu2, Cp′′′=1,2,4‐C5H2tBu3) turned out to be predestined for the formation of hollow spherical supramolecules with non‐classical fullerene‐like topology. The resulting assemblies constructed with CuX (X=Cl, Br) showed a highly symmetric 32‐vertex core of solely four‐ and six‐membered rings. In some supramolecules, the inner cavity was occupied by an additional CuX unit. On the other hand, using CuI, two different supramolecules with either peanut‐ or pear‐like shapes and outer diameters in the range of 2–2.5 nm were isolated. Furthermore, the spherical supramolecules containing Cp′′′ ligands at tantalum are soluble in CH2Cl2. NMR spectroscopic investigations in solution revealed the formation of isomeric supramolecules owing to the steric hindrance caused by the third tBu group on the Cp′′′ ligand. In addition, a 2D coordination polymer was obtained and structurally characterized.

Discrete and Polymeric Organometallic‐Organic Hybrid Materials Based on the Diphosphorus Complex [Cp2Mo2(CO)4(η2‐P2)], CuI Salts, and 2,2′‐Bipyrimidine

“…In contrast to typical approaches in this area, in which nitrogen‐, oxygen‐, or sulfur‐donor‐containing organic ligands are employed to connect different metal centers, our group established an alternative approach by utilizing organometallic polyphosphorus (P n ) ligand complexes with flexible coordination modes as connectors between metal ions. This novel method allows for the synthesis of 1D and 2D coordination polymers, nano‐sized fullerene‐like supramolecular spherical aggregates, and a huge molecular organometallic capsule . An alternative approach by using three‐component reactions was also developed in our group.…”

Transition metal complexes of the naked pnictide elements

“…114 Cp'''(CO)2TaP4 ( Figure 78G) rises from the reaction of Cp'''Ta(CO)4 with P4 in toluene and is one of the few early transition metal compounds in this class. 112 A similarly simple complex arises from the reaction of (Cp'''Co)2(C7H8) with P4 ( Figure 78H). 117 The product Cp'''CoP4 readily dimerizes in solution to give compounds with P8 units.…”

“…Regular cyclo-P4 units are seen in Cp'''(CO)2TaP4, 112 Cp"FeP4{Fe(CO)2Cp"}, 113 (Ph5C5)CoP4{Cr(CO)5}3 114 and (1,2,4-t Bu3H2C5)CoP4{Cr(CO)5}3. 114 Cp'''(CO)2TaP4 ( Figure 78G) rises from the reaction of Cp'''Ta(CO)4 with P4 in toluene and is one of the few early transition metal compounds in this class.…”

“…The distances are L2Cr2P4, 1.8664(8) Å; L2Cr2P4W(CO)5, 1.9038(6) Å; L2Cr2P3As, 1.8735(5) Å; L2Cr2As4, 1.863(2) Å. 112 and show Fullerene-like cage structures built on the ME4-Cu networks. For the same reaction under different conditions, a 2-dimensional polymeric structure was also obtained.…”

Reappraising Schmidpeter's bis(iminophosphoranyl)phosphides: coordination to transition metals and bonding analysis

“…These are rare examples of structurally characterized examples of d 0 /d 10 heterobimetallic complexes bridged by a phosphorus atom. [79][80][81][82][83] Both complexes show some disorder (the t Bu group in the case of 7b, one of the Ph groups in the case of 8b).…”