Chemical transformations on phosphido- and phosphinidene-bridged ruthenium clusters
Novel examples of P-C bond activation under mild conditions are reported. The reactions of phosphinoalkynes Ph[sub 2]PC[triple bond]CR (R = Ph, Bu[sup t], Pr[sup i]) with the formally 46 electron cluster ([mu]-H)Ru[sub 3](CO)[sub 9]([mu]-PPh[sub 2]) 2 results in P-C bond cleavage, transfer of a phosphido group onto the cluster, and transfer of a hydride to the acetylide. The new species Ru[sub 3](CO)[sub 7]([mu]-PPh[sub 2])[sub 2]([mu][sub 3]-[eta][sup 2]-HC[triple bond]CR) 5a-c are representatives of a new class of [mu][sub 3]-[eta][sup 2]-[parallel] acetylene clusters with NIDO 5 vertex structures. The reaction of PhC[triple bond]CPh with ([mu]-H)Ru[sub 3](CO)[sub 7]([mu]-PPh[sub 2])[sub 3] 6 provides a general high yield route to the class of metallocarbonphosphorus clusters through the direct synthesis of an MMP(R)C(R)C(R) system from a [mu]-diphenylphosphido group. The chemistry of M[sub 4] butterfly carbides and nitrides has proven that a butterfly framework allows unusual patterns of chemical reactivity. The structures of Ru[sub 4](CO)[sub 12]([mu][sub 3]-PPh)(Me[sub 2]PPh), Ru[sub 4](CO)[sub 10]([mu][sub 3]-PPh)([eta][sup 6]-tol), H[sub 2]Ru[sub 4](CO)[sub 12]([mu][sub 3]-PPh) and Ru[sub 4](CO)[sub 11]([mu][sub 4]-PPh)([mu][sub 4]-S) have been determined by X-ray analysis. The pyrolysis of ([mu]-H)Ru[sub 3](CO)[sub 10]([mu]-PPh[sub 2]) in toluene afforded a range of products from which the first heptaruthenium cluster Ru[sub 7](CO)[sub 18]([mu][sub 4]-PPh)[sub 2] 33 and Ru[sub 8](CO)[sub 21]([mu][sub 6]-P)([mu][sub 4]-PPh)([mu]-PPh[sub 2]) 32 have been isolated. X-ray analysis has revealed that 33 possesses a novel condensed metal framework based on 2 square pyramidal Ru[sub 5] fragments sharing a common face. The structure of 32 confirms the ability of the phosphide atom to exist in a greater variety of partially exposed cluster environments that carbides and nitrides.
- Research Organization:
- Waterloo Univ., ON (Canada)
- OSTI ID:
- 5517754
- Country of Publication:
- United States
- Language:
- English
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Chemical transformations on phosphido-bridged clusters. Methyne, methylene transfer, and ketene forming reactions involving the. mu. methylene cluster Ru/sub 3/(CO)/sub 7/(. mu. -CH/sub 2/)/. mu. /sub 3/-eta/sup 3/-CH/sub 2/ =C=C(i-Pr)/(. mu. -PPh/sub 2/). X-ray structures of (. mu. -H)Ru/sub 3/(CO)/sub 7//. mu. /sub 3/-eta/sup 4/-CH=C(i-Pr)C=CH/sub 2//(. mu. -PPH/sub 2/) and Ru/sub 3/(CO)/sub 6/(. mu. -CO)/. mu. /sub 3/-eta/sup 4/-CH/sub 2/=C(i-Pr)C=CH/sub 2//(PPh/sub 3/)(. mu. -PPH/sub 2/)
Reactions of HC triple bond CCMe sub 2 NHCOR alkynes with M sub 3 (CO) sub 12 carbonyls (M = Ru, R = C sub 6 H sub 9 , Ph; M = Os, R = C sub 6 H sub 9 ). Synthesis and crystal structure of Ru sub 4 (CO) sub 11 (HC triple bond CCMe sub 2 NHCOC sub 6 H sub 9 ), a butterfly cluster showing an interaction between a wingtip metal and the amide CO
Related Subjects
400100 -- Analytical & Separations Chemistry
400200* -- Inorganic
Organic
& Physical Chemistry
CARBON
CHEMICAL BONDS
CHEMICAL PREPARATION
COHERENT SCATTERING
CRYSTAL STRUCTURE
DIFFRACTION
ELEMENTS
MOLECULAR CLUSTERS
MOLECULAR STRUCTURE
NONMETALS
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOSPHORUS
REFRACTORY METAL COMPOUNDS
RUTHENIUM COMPOUNDS
SCATTERING
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION