title: Methylation of [Pt₂(μ-SR) (μ-S) (PPh₃)₄]: en route to mixed-thiolato bridged complexes

authors: Chong, Siew Huay

subjects: alkylation

abstract: Sequential and independent alkylation of [Pt₂(μ-SR) (μ-S) (PPh₃)₄] by RX followed by methylation with Me₂SO₄ led to the first successful isolation of novel diplatinum complexes [Pt₂(μ-SR) (μ -SCH₃) (PPh₃)₄](PF₆)₂ (3) (R= CH₂C₆H₅(a), CH₂CHCH₂ (b), C₅H₁₀CO₂CH₂CH₃(c), C₂H₄CO₂- CH₂CH₃(d), CH₂CH₂CN (e), C₂H₄CH-(O)₂C₂H₄ (f), and C₂H₄SC₆H₅(g)) with asymmetric thiolato bridges. The synthetic methodology can tolerate a range of electronically and sterically contrasting thiolate substituents with different chemical functionalities. The X-ray crystal structures of 3 a–c, g confirm the unusual heterodialkylation with two different thiolato bridging ligands in a syn–exo conformation. A secondary product [Pt₂(μ-SC₂H₄SC₆H₅) (μ-SCH₃)(PPh₃)₃](PF₆)₂ (4), which arises from intramolecular phosphine displacement by the thio pendant at the neighboring SC₂H₄SC₆H₅bridge, has been trapped and characterized. This is an unusual diplatinum complex with three different bridging thio ligands and three different phosphines.
The heteroalkylation is screened in situ by ESI-MS, and the resultant spectral data provide a convenient guide for one-pot syntheses of {M₂(SR) (SR’)} from {M₂S}. The isolation and X-ray crystal structure of a homoalkylated analogue [Pt₂(μ-SCH₃)₂(PPh₃)₄](PF₆)₂ (6) is included for comparison.

text: Methylation of [Pt₂(μ-SR) (μ-S) (PPh₃)₄]: en route to mixed-thiolato bridged complexes Sequential and independent alkylation of [Pt₂(μ-SR) (μ-S) (PPh₃)₄] by RX followed by methylation with Me₂SO₄ led to the first successful isolation of novel diplatinum complexes [Pt₂(μ-SR) (μ -SCH₃) (PPh₃)₄](PF₆)₂ (3) (R= CH₂C₆H₅(a), CH₂CHCH₂ (b), C₅H₁₀CO₂CH₂CH₃(c), C₂H₄CO₂- CH₂CH₃(d), CH₂CH₂CN (e), C₂H₄CH-(O)₂C₂H₄ (f), and C₂H₄SC₆H₅(g)) with asymmetric thiolato bridges. The synthetic methodology can tolerate a range of electronically and sterically contrasting thiolate substituents with different chemical functionalities. The X-ray crystal structures of 3 a–c, g confirm the unusual heterodialkylation with two different thiolato bridging ligands in a syn–exo conformation. A secondary product [Pt₂(μ-SC₂H₄SC₆H₅) (μ-SCH₃)(PPh₃)₃](PF₆)₂ (4), which arises from intramolecular phosphine displacement by the thio pendant at the neighboring SC₂H₄SC₆H₅bridge, has been trapped and characterized. This is an unusual diplatinum complex with three different bridging thio ligands and three different phosphines.
The heteroalkylation is screened in situ by ESI-MS, and the resultant spectral data provide a convenient guide for one-pot syntheses of {M₂(SR) (SR’)} from {M₂S}. The isolation and X-ray crystal structure of a homoalkylated analogue [Pt₂(μ-SCH₃)₂(PPh₃)₄](PF₆)₂ (6) is included for comparison.

year: 2006

title: A computational study of the oxidation of SO₂ to SO₃ by gas-phase organic oxidants

authors: Kurten, Theo

subjects: chemistry

abstract: We have studied the oxidation of SO₂ to SO₃ by four peroxyradicals and two carbonyl oxides (Criegee intermediates) using both density functional theory, B3LYP, and explicitly correlated coupled cluster theory, CCSD(T)-F12. All the studied peroxyradicals react very slowly with SO₂  due to energy barriers (activation energies) of around 10 kcal/mol or more. We find that water molecules are not able to catalyze these reactions. The reaction of stabilized Criegee intermediates with SO₂  is predicted to be fast, as the transition states for these oxidation reactions are below the free reactants in energy. The atmospheric relevance of these reactions depends on the lifetimes of the Criegee intermediates, which, at present, is highly uncertain.

text: A computational study of the oxidation of SO₂ to SO₃ by gas-phase organic oxidants We have studied the oxidation of SO₂ to SO₃ by four peroxyradicals and two carbonyl oxides (Criegee intermediates) using both density functional theory, B3LYP, and explicitly correlated coupled cluster theory, CCSD(T)-F12. All the studied peroxyradicals react very slowly with SO₂  due to energy barriers (activation energies) of around 10 kcal/mol or more. We find that water molecules are not able to catalyze these reactions. The reaction of stabilized Criegee intermediates with SO₂  is predicted to be fast, as the transition states for these oxidation reactions are below the free reactants in energy. The atmospheric relevance of these reactions depends on the lifetimes of the Criegee intermediates, which, at present, is highly uncertain.

year: 2011

title: Kapa Haka Whakataetae Kua tini haere te kanohi o te mahi kapa haka i te ao hurihuri nei.

authors: Rollo, Te Manaaroha Pirihira

subjects: Kapa Haka

abstract: Tihei Haka! Mauriora Kapa haka (Rollo, 2006)
Ka tū te ihiihi, ka tū te wanawana o te hunga i ngā hui whakataetae kapa haka o te motu. He hui rongonui i te maramataka a te Māori ia tau ia tau, ā, he hui whakahirahira anō mō rātou mā i whakawhiti mai i tāwahi rā hoki. Mā te mahi a te kapa haka ka whakaari ngā rōpū haka i ngā mahi nō nehe rā me ngā mahi hou o te ao onāianei. Ahakoa te āhuatanga o te mahi, he taonga tuku iho nā rātou mā kua mene ki te pō.  Moe mai rā e te kāhui o ngā whetu i te pō, moe mai i te Ariki o te rangi. 

I tēnei tuhinga, e āta titiro ana 'hau ki ngā mahi hou me te āhuatanga hou kei ngā rōpū haka i te whakataetae-a-motu, arā Te Matatini me ētahi atu momo whakataetae i Aotearoa, tāpiri mai hoki ērā kei Te Moana nui a Kiwa. Ko te ingoa matua o tēnei tuhinga,  KAPA HAKA WHAKATAETAE. Kua tīni haere te kanohi o te mahi kapa haka i te ao hurihuri nei .
No reira, ko te tino pātai kei tēnei rangahau ko tērā. He aha ngā mahi hou kei te kapa haka whakataetae? Nā he hua anō hoki kei reira? Ka hāngaia tonu e te tuhinga nei  ngā hui whakataetae kapa haka mai i te tau 1972 tae noa ki te tau 2006.

Ngā ūpoko o te tuhinga whakapae
E whā ngā wāhanga ūpoko o tēnei tuhinga whakapae. Mā ngā ūpoko katoa ka kitea ai ngā momo kaupapa ake e hāngai pū ana ki te kaupapa mō te whakataetae kapa haka me ōna āhuatanga hou. He mahi whakahirahira tāku ki te whakatakoto i ngā kōrero, i ngā whakaaro, i ngā mātauranga o tēnā tangata mōhio, o tēnā tangata mātau ki roto i ngā whare māramatanga, arā ngā  wāhanga wēnā,  hei mātauranga hou mō te ao katoa.

I te ūpoko tuatahi, ka anga te titiro ki ngā whakamāramatanga o ngā tikanga-a-iwi e pā ana ki te  tūturutanga me te ao o te kapa haka. Mā wēnei whakamāramatanga hei awhi i a 'hau i taku rangahau ki te mahi onāianei o te whakataetae kapa haka. Ka whai mātauranga 'hau mō ngā tikanga o ngā kupu e rua. Ko ēnei ko te kupu  haka  te tuatahi, ā, ko te kupu  kapa haka  te tuarua. He aha ngā rerekētanga me te ōritenga o wēnei kupu rongonui? Ka anga whakamua ki ngā tūmanako me ngā ritenga o te whakataetae kapa haka a te motu mai i te New Zealand Polynesian Festival tae atu ki Te Matatini. Ko te whāinga mutunga o tēnei wāhanga, ka hoki whakanui ki te whakataetae-a-motu mai i te tau 1972 tae noa atu ki te tau 2006.

Ko te ūpoko tuarua, ka whakatakoto e 'hau ngā whakautu o ngā patapātai mai i ngā rārangi kōrero me ngā whakaaro whānui i whakahokia mai e ngā tāngata o ngā rōpū haka e whā, arā, Te Rōpū Haka o Te Kotahitanga, Ngāti Poneke Young Māori Club, ko Te Waihīrere, ā, huri atu ki Te Pou a Mangatāwhiri hoki, he rōpū i whakatūhia anō i te tau 2005. I tēnei wāhanga ka kitea ngā kōrero ātaahua, ngā mātauranga tūturu me ngā whakaaro hōhonu o ngā kaiako me ngā tāngata e tautoko ana i taku mahi kimi mātauranga.  Nā rātou ka ohorere, ka mirimiri hoki i tōku hinengaro ki ngā māramatanga hou. He tika anō te kupu ā  Pā Henare Tate nō Ngapuhi nui tonu e kī ana,  Mā te whakaatu, ka mōhio, mā te mōhio, ka mārama, mā te mārama, ka mātau, mā te mātau, ka ora   (Barlow 1991)

I te ūpoko tuatoru he whakaaturanga tēnei o āku tirohanga ki ngā āhua rerekē me ngā mahi hou i roto i ngā rōpū haka i runga i te ātamira o te whakataetae, i roto hoki i te mura o te ahi o te whakataetae. Kua tuhituhi au i ngā momo āhuatanga e pā ana ki  te taha o te kanikani, te mahi-a-korikori me ngā mahi katoa i runga i te atamira. Ahakoa iti ko tētahi atu wahanga o ērā kōrero e pā ana ki te pūoro me ōna mana kua puta i konei. Ka huri taku tuhinga ki te taha o te reo waiata, te toi whakaari me te whakaataata o ngā mahi a te Rēhia. I konei ka titiro ki te tāmoko, te pani kanohi me te pani tinana, arā he mahi hou katoa. Ko te wahanga mutunga e pā ana ki te reo Māori me te tito waiata hoki. Ahakoa he maha ngā āhuatanga, ko ngā tuhinga nei mō ia āhuatanga kia kitea ai ngā rerekēnga me ngā mahi hou i te whakataetae kapa haka o te ao Māori. No reira te nuinga engari ko wētahi i whakaurua mai i ētahi atu iwi ō tāwahi.       

Ko te ūpoko whakamutunga, ka hāngai taku titiro ki te ao o te whakataetae, arā, ki ngā whakaaro me te tā o te hinengaro me te ngākau o te tangata. Ka peka haere ki te whakatū o ngā rōpū whakataetae me te parakatihi o ngā waiata, ngā haka me ngā whakaritenga mo te whakataetae kapa haka. Ko te kōrero whakamutunga, ka huri ki wētahi atu o ngā whakataetae mai i Te Kuki Airani, i Tahiti me Hawaii hoki. Āe mārika, ka ora te ao o te whakataetae puta noa i te ao nui. Ki ahau, mā tēnei tuhinga hei whakapuare ngā hurihanga o te ao Māori me te ao o te kapa haka. Ka ea, he tika hoki te whakataukī rā,  ka pū te ruha, ka hao te rangatahi    (Ryan 1995), arā ka kimi i ērā e pīataata ai o rātou wairua, hinengaro, ngākau.

text: Kapa Haka Whakataetae Kua tini haere te kanohi o te mahi kapa haka i te ao hurihuri nei. Tihei Haka! Mauriora Kapa haka (Rollo, 2006)
Ka tū te ihiihi, ka tū te wanawana o te hunga i ngā hui whakataetae kapa haka o te motu. He hui rongonui i te maramataka a te Māori ia tau ia tau, ā, he hui whakahirahira anō mō rātou mā i whakawhiti mai i tāwahi rā hoki. Mā te mahi a te kapa haka ka whakaari ngā rōpū haka i ngā mahi nō nehe rā me ngā mahi hou o te ao onāianei. Ahakoa te āhuatanga o te mahi, he taonga tuku iho nā rātou mā kua mene ki te pō.  Moe mai rā e te kāhui o ngā whetu i te pō, moe mai i te Ariki o te rangi. 

I tēnei tuhinga, e āta titiro ana 'hau ki ngā mahi hou me te āhuatanga hou kei ngā rōpū haka i te whakataetae-a-motu, arā Te Matatini me ētahi atu momo whakataetae i Aotearoa, tāpiri mai hoki ērā kei Te Moana nui a Kiwa. Ko te ingoa matua o tēnei tuhinga,  KAPA HAKA WHAKATAETAE. Kua tīni haere te kanohi o te mahi kapa haka i te ao hurihuri nei .
No reira, ko te tino pātai kei tēnei rangahau ko tērā. He aha ngā mahi hou kei te kapa haka whakataetae? Nā he hua anō hoki kei reira? Ka hāngaia tonu e te tuhinga nei  ngā hui whakataetae kapa haka mai i te tau 1972 tae noa ki te tau 2006.

Ngā ūpoko o te tuhinga whakapae
E whā ngā wāhanga ūpoko o tēnei tuhinga whakapae. Mā ngā ūpoko katoa ka kitea ai ngā momo kaupapa ake e hāngai pū ana ki te kaupapa mō te whakataetae kapa haka me ōna āhuatanga hou. He mahi whakahirahira tāku ki te whakatakoto i ngā kōrero, i ngā whakaaro, i ngā mātauranga o tēnā tangata mōhio, o tēnā tangata mātau ki roto i ngā whare māramatanga, arā ngā  wāhanga wēnā,  hei mātauranga hou mō te ao katoa.

I te ūpoko tuatahi, ka anga te titiro ki ngā whakamāramatanga o ngā tikanga-a-iwi e pā ana ki te  tūturutanga me te ao o te kapa haka. Mā wēnei whakamāramatanga hei awhi i a 'hau i taku rangahau ki te mahi onāianei o te whakataetae kapa haka. Ka whai mātauranga 'hau mō ngā tikanga o ngā kupu e rua. Ko ēnei ko te kupu  haka  te tuatahi, ā, ko te kupu  kapa haka  te tuarua. He aha ngā rerekētanga me te ōritenga o wēnei kupu rongonui? Ka anga whakamua ki ngā tūmanako me ngā ritenga o te whakataetae kapa haka a te motu mai i te New Zealand Polynesian Festival tae atu ki Te Matatini. Ko te whāinga mutunga o tēnei wāhanga, ka hoki whakanui ki te whakataetae-a-motu mai i te tau 1972 tae noa atu ki te tau 2006.

Ko te ūpoko tuarua, ka whakatakoto e 'hau ngā whakautu o ngā patapātai mai i ngā rārangi kōrero me ngā whakaaro whānui i whakahokia mai e ngā tāngata o ngā rōpū haka e whā, arā, Te Rōpū Haka o Te Kotahitanga, Ngāti Poneke Young Māori Club, ko Te Waihīrere, ā, huri atu ki Te Pou a Mangatāwhiri hoki, he rōpū i whakatūhia anō i te tau 2005. I tēnei wāhanga ka kitea ngā kōrero ātaahua, ngā mātauranga tūturu me ngā whakaaro hōhonu o ngā kaiako me ngā tāngata e tautoko ana i taku mahi kimi mātauranga.  Nā rātou ka ohorere, ka mirimiri hoki i tōku hinengaro ki ngā māramatanga hou. He tika anō te kupu ā  Pā Henare Tate nō Ngapuhi nui tonu e kī ana,  Mā te whakaatu, ka mōhio, mā te mōhio, ka mārama, mā te mārama, ka mātau, mā te mātau, ka ora   (Barlow 1991)

I te ūpoko tuatoru he whakaaturanga tēnei o āku tirohanga ki ngā āhua rerekē me ngā mahi hou i roto i ngā rōpū haka i runga i te ātamira o te whakataetae, i roto hoki i te mura o te ahi o te whakataetae. Kua tuhituhi au i ngā momo āhuatanga e pā ana ki  te taha o te kanikani, te mahi-a-korikori me ngā mahi katoa i runga i te atamira. Ahakoa iti ko tētahi atu wahanga o ērā kōrero e pā ana ki te pūoro me ōna mana kua puta i konei. Ka huri taku tuhinga ki te taha o te reo waiata, te toi whakaari me te whakaataata o ngā mahi a te Rēhia. I konei ka titiro ki te tāmoko, te pani kanohi me te pani tinana, arā he mahi hou katoa. Ko te wahanga mutunga e pā ana ki te reo Māori me te tito waiata hoki. Ahakoa he maha ngā āhuatanga, ko ngā tuhinga nei mō ia āhuatanga kia kitea ai ngā rerekēnga me ngā mahi hou i te whakataetae kapa haka o te ao Māori. No reira te nuinga engari ko wētahi i whakaurua mai i ētahi atu iwi ō tāwahi.       

Ko te ūpoko whakamutunga, ka hāngai taku titiro ki te ao o te whakataetae, arā, ki ngā whakaaro me te tā o te hinengaro me te ngākau o te tangata. Ka peka haere ki te whakatū o ngā rōpū whakataetae me te parakatihi o ngā waiata, ngā haka me ngā whakaritenga mo te whakataetae kapa haka. Ko te kōrero whakamutunga, ka huri ki wētahi atu o ngā whakataetae mai i Te Kuki Airani, i Tahiti me Hawaii hoki. Āe mārika, ka ora te ao o te whakataetae puta noa i te ao nui. Ki ahau, mā tēnei tuhinga hei whakapuare ngā hurihanga o te ao Māori me te ao o te kapa haka. Ka ea, he tika hoki te whakataukī rā,  ka pū te ruha, ka hao te rangatahi    (Ryan 1995), arā ka kimi i ērā e pīataata ai o rātou wairua, hinengaro, ngākau.

year: 2007