TY - JOUR
T1 - Synthesis of mercury-linked ruthenium clusters
T2 - The X-ray structure of the new cluster dianion [{Ru6C(CO)16}2Hg]2- and the cluster [{Ru5C(CO)14(μ-Cl)}2Hg2Cl 2]
AU - Johnson, Brian F.G.
AU - Kwik, Whei Lu
AU - Lewis, Jack
AU - Raithby, Paul R.
AU - Saharan, Vijay P.
PY - 1991/1/1
Y1 - 1991/1/1
N2 - Reaction of the hexaruthenium dianion [Ru6C(CO)16]2- 1 as its [N(PPh3)2]+ salt in CH2Cl2 with an equimolar quantity of Hg(CF3CO2)2 leads to an uncharacterised black polymer of probable formula [Ru6C(CO)16Hg]n. However, treatment of 2 equivalents of 1 in CH2Cl2 with 1 equivalent of Hg(CF3CO2)2 or 2 equivalents of HgCl2 in the same solvent has yielded the new dodecaruthenium dianion [{Ru6C(CO)16}2Hg]2- 2. This red dianion has been characterised as its [N(PPh3)2]+ salt by single-crystal X-ray diffraction analysis and shown to contain two octahedral Ru6C units linked through a mercury atom. It is probably produced from the uncharacterised intermediate monoanion [Ru6C(CO)16(HgX)]- 3a (X = Cl or CF3CO2). In agreement with this suggestion, treatment of 1 with the compound Hg(CF3)(CF3CO2) yields the monoanion [Ru6C(CO)16(HgCF3)]- 3b which has been fully characterised on the basis of its spectroscopic data. We have also observed that the neutral pentaruthenium cluster [Ru5C(CO)15] 4 reacts with HgCl2 to produce the dark red decaruthenium species [{Ru5C(CO)14(μ-Cl)}2Hg2Cl 2] 5. On the basis of single-crystal X-ray diffraction analysis this cluster has been shown to consist of two distorted bridged-butterfly Ru5C(CO)14(μ-Cl) units linked by a Hg2(μ-Cl)2 unit. In solution, it appears that the dimeric cluster 5 undergoes dissociation to a monomer believed to be [Ru5C(CO)14(μ-Cl)(HgCl)] 6. The mass spectrum of cluster 5 is not totally consistent with this unit and in the fast atom bombardment mass spectrum, the ion corresponding to [Ru5C(CO)13(μ-Cl)(HgCl)] 7 is observed.
AB - Reaction of the hexaruthenium dianion [Ru6C(CO)16]2- 1 as its [N(PPh3)2]+ salt in CH2Cl2 with an equimolar quantity of Hg(CF3CO2)2 leads to an uncharacterised black polymer of probable formula [Ru6C(CO)16Hg]n. However, treatment of 2 equivalents of 1 in CH2Cl2 with 1 equivalent of Hg(CF3CO2)2 or 2 equivalents of HgCl2 in the same solvent has yielded the new dodecaruthenium dianion [{Ru6C(CO)16}2Hg]2- 2. This red dianion has been characterised as its [N(PPh3)2]+ salt by single-crystal X-ray diffraction analysis and shown to contain two octahedral Ru6C units linked through a mercury atom. It is probably produced from the uncharacterised intermediate monoanion [Ru6C(CO)16(HgX)]- 3a (X = Cl or CF3CO2). In agreement with this suggestion, treatment of 1 with the compound Hg(CF3)(CF3CO2) yields the monoanion [Ru6C(CO)16(HgCF3)]- 3b which has been fully characterised on the basis of its spectroscopic data. We have also observed that the neutral pentaruthenium cluster [Ru5C(CO)15] 4 reacts with HgCl2 to produce the dark red decaruthenium species [{Ru5C(CO)14(μ-Cl)}2Hg2Cl 2] 5. On the basis of single-crystal X-ray diffraction analysis this cluster has been shown to consist of two distorted bridged-butterfly Ru5C(CO)14(μ-Cl) units linked by a Hg2(μ-Cl)2 unit. In solution, it appears that the dimeric cluster 5 undergoes dissociation to a monomer believed to be [Ru5C(CO)14(μ-Cl)(HgCl)] 6. The mass spectrum of cluster 5 is not totally consistent with this unit and in the fast atom bombardment mass spectrum, the ion corresponding to [Ru5C(CO)13(μ-Cl)(HgCl)] 7 is observed.
UR - http://www.scopus.com/inward/record.url?scp=37049087795&partnerID=8YFLogxK
U2 - 10.1039/DT9910001037
DO - 10.1039/DT9910001037
M3 - Article
AN - SCOPUS:37049087795
SN - 1472-7773
SP - 1037
EP - 1042
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 4
ER -