Tri(2-furyl)phosphine (PFu 3) reacts with [Ru 4(μ-H) 4(CO) 12] (1) in refluxing THF to give, apart from an isomeric pair of the substituton products [Ru 4(μ-H) 4(CO) 10(PFu 3) 2] (2a and 2b), the μ-phosphido cluster [Ru 4(μ-H) 2(CO) 8(PFu 3) 2(μ-PFu 2)(μ-n 1,n 2-C 4H 3O)] (3) and a series of μ 3- and μ 4-phosphinidene clusters [Ru 4(μ-H) 2(CO) 12-x(PFu 3) x(μ 3-PFu)] (x = 0 (4), 2 (5), 3 (6)) and [Ru 4(μ-H) 2(CO) 9(PFu 3) 2(μ 4-PFu)(μ 3-n 1,n 1,n 2-C 4H 2O)] (7). In this one-pot reaction, the excellent facility for PFu 3 to act as rich sources of furyl, furyne, phosphide (μ-PR 2), and phosphinidene (μ 3-PR and μ 4-PR) fragments on tetrametallic frameworks has been demon-strated. The single-crystal X-ray structures of all new molecules have been determined. The structure of 7 represents the first structurally characterized example of stable furyne-containing cluster complexes of ruthenium. The electrochemical behavior and molecular orbital calculations of these metallophosphorus clusters have been examined as a function of the coordination modes of the phosphorus-containing moieties.
Scopus Subject Areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry